JP6006738B2 - Adhesive phosphorescent composite sheet - Google Patents

Description

  The present invention relates to an adhesive phosphorescent composite sheet.

Conventionally, a sheet or flooring using a phosphorescent material has been put into practical use.
Such sheets and flooring materials are used for disaster prevention and safety signs and various guide signs by utilizing the property that a luminous material that absorbs light energy emits light in the dark. When the phosphorescent material emits light, if a layer for concealing light is provided on the back surface of the phosphorescent material, the phosphorescent performance is further improved. Therefore, a concealing layer is provided on the back surface of the layer containing the phosphorescent material. Sometimes. In this case, a pressure-sensitive adhesive layer is further provided on such a concealing layer.

  Patent Document 1 describes a phosphorescent silicone rubber sheet having a phosphorescent layer containing a phosphorescent substance in silicone rubber, a reflective layer containing a white pigment in silicone rubber, and an adhesive layer. Patent Document 2 describes a luminescent composite sheet in which a backing material, a base synthetic resin layer, a colored synthetic resin layer, and a luminescent pigment-containing synthetic resin layer are laminated and integrated. Patent Document 3 describes a laminate composite sheet having an organic pressure-sensitive adhesive layer. However, this type of conventional composite sheet is inferior in long-term sticking stability and in particular in re-sticking property.

  In order to solve this problem, Patent Document 4 uses a silicone rubber layer and a silicone gel layer to provide flexibility, weather resistance, reworkability, and without causing a decrease in adhesive strength over a long period of time. A laminate composite sheet has been proposed. However, even in this composite sheet, the wettability between the silicone and the phosphorescent agent is not good, and there is a problem that the emission intensity is lowered due to light scattering and attenuation at the interface with the silicone. In addition, there is a problem in that the moisture is adsorbed on the surface of the phosphorescent agent under high temperature and high humidity, and the emission intensity decreases.

JP 2007-118203 A JP 10-1114030 A JP 2010-137470 A JP 2012-153129 A

  The present invention has been made in view of the above circumstances, has flexibility, is excellent in weather resistance and reworkability, can be used without causing a decrease in adhesive force over a long period of time, and can be reattached even after peeling. It is an object of the present invention to provide an adhesive phosphorescent composite sheet that can be attached, can be used repeatedly, has a long phosphorescence time, and does not cause a decrease in light emission intensity over a long period even under high temperature and high humidity.

In order to solve the above problems, in the present invention, an adhesive phosphorescent composite sheet in which an adhesive layer made of an adhesive silicone resin or gel is laminated on a base rubber in which a phosphorescent agent is dispersed,
The base rubber is
(I) Silicone rubber substrate having a JIS-A hardness of 10 to 90 after curing: 100 parts by mass
(II) Luminescent agent: 5-1000 parts by mass,
(III) An adhesive luminescent composite sheet characterized by comprising alkoxysilane or hydrolyzable methylpolysiloxane or both: 0.1 to 10 parts by mass.

  If it is such an adhesive phosphorescent composite sheet, it has flexibility, excellent weather resistance and reworkability, and can be used without causing a decrease in adhesive force over a long period of time. It can be used repeatedly, has a long light storage time, and does not cause a decrease in light emission intensity over a long period even under high temperature and high humidity.

Further, the alkoxysilane in the component (III) is represented by the following general formula (1)
R ¹ _a R ² _b Si (OR ³ ) _4-ab (1)
(Wherein R ¹ is an alkyl group having 6 to 15 carbon atoms, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ³ is an alkyl group having 1 to 6 carbon atoms, and a is An integer of 1 to 3, b is an integer of 0 to 2, and a + b is an integer of 1 to 3.)
It is preferable that it is represented by these.

（式中、Ｒ^４は炭素数１〜６のアルキル基、ｃは５〜１００の整数である。）
で表される片末端３官能の加水分解性メチルポリシロキサンであることが好ましい。 The hydrolyzable methylpolysiloxane in the component (III) is represented by the following general formula (2)

(In the formula, R ⁴ is an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100.)
Is preferably a trifunctional hydrolyzable methylpolysiloxane represented by formula (1).

  By using such a compound, the affinity between the phosphorescent agent in the base rubber and the rubber substrate can be further improved, and the phosphorescent agent can be uniformly dispersed in the rubber substrate.

The phosphorescent agent is represented by the general formula: MAl ₂ O ₄ · X _K · Y _L · Z _P [wherein M is one or more selected from the group consisting of calcium, barium, strontium, magnesium and mixtures thereof. Metal, X is an activator comprising europium, Y and Z are activators made of elements selected from the group of lanthanum series elements and manganese, tin and bismuth, respectively. 001 to 10, L represents 0 to 10 in terms of mol% relative to M, and P represents 0 to 10 in terms of mol% based on M. It is preferable that the average particle size of the phosphor is 0.1 to 70 μm.

  By using such a compound, the afterglow brightness | luminance of an adhesive light storage composite sheet can be made larger, and the afterglow time can also be made longer.

Further, the pressure-sensitive adhesive layer is (A) an organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms on average in one molecule: 10 to 75 parts by mass,
(C) R ′ ₃ SiO _1/2 unit (wherein R ′ is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, R ′ ₃ SiO _1/2 unit and SiO ₂ unit And the molar ratio [R ′ ₃ SiO _1/2 / SiO ₂ ] is 0.5 to 1.5, R ′ contains an alkenyl group, and the total amount thereof is 0.0001 mol / g or more. Combined: 5-50 parts by mass,
(D) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule: 0.5 to 30 mass with respect to 100 mass parts in total of the component (A) and the component (C) And the amount of hydrogen atoms bonded to silicon atoms in component (D) relative to alkenyl groups bonded to silicon atoms contained in components (A) and (C) is 0.32 in molar ratio. An amount of ~ 0.75,
(E) Addition reaction catalyst: It is composed of a cured product of an addition-curable silicone rubber composition containing a catalytic amount, and the cured product preferably has surface tackiness.

  By using a cured product of such a composition as an adhesive layer, while having a certain rubber hardness and rubber strength, an adhesive phosphorescent composite sheet having adhesiveness that can be adhered and fixed to a substrate and various parts, and can do.

  Moreover, it is preferable that the hardness of the said adhesion layer is lower than the hardness of the said base rubber, and the penetration degree prescribed | regulated to JISK2220 of the said adhesion layer is 1-100.

  Thus, if the penetration of the adhesive layer is within the above range, an adhesive phosphorescent composite sheet having sufficient adhesiveness and rubber strength is preferable.

Further, the pressure-sensitive adhesive layer is (A) an organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms on average in one molecule: 10 to 75 parts by mass,
(B) R ₃ SiO _1/2 unit (wherein R is an unsubstituted or substituted monovalent hydrocarbon group) and a SiO ₂ unit as main components, and the moles of R ₃ SiO _1/2 unit and SiO ₂ unit A resin material having a ratio [R ₃ SiO _1/2 / SiO ₂ ] of 0.5 to 1.5 and R does not contain an alkenyl group or the total amount is less than 0.0001 mol / g. Polymer: 20 to 70 parts by mass,
(C) R ′ ₃ SiO _1/2 unit (wherein R ′ is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, R ′ ₃ SiO _1/2 unit and SiO ₂ unit And the molar ratio [R ′ ₃ SiO _1/2 / SiO ₂ ] is 0.5 to 1.5, R ′ contains an alkenyl group, and the total amount thereof is 0.0001 mol / g or more. Combined: 5-50 parts by mass,
(D) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule: 100 parts by mass in total of the component (A), the component (B), and the component (C) And 0.5 to 30 parts by mass of the silicon atom in the component (D) with respect to the alkenyl group bonded to the silicon atom contained in the component (A), the component (B), and the component (C). The amount of hydrogen atoms bonded to is such that the molar ratio is 0.32-0.75,
(E) Addition reaction catalyst: It is composed of a cured product of an addition-curable silicone rubber composition containing a catalytic amount, and the cured product preferably has surface tackiness.

  By using a cured product of such a composition as an adhesive layer, while having a certain rubber hardness and rubber strength, an adhesive phosphorescent composite sheet having adhesiveness that can be adhered and fixed to a substrate and various parts, and can do. In particular, by including the component (B) in the composition, more sufficient adhesiveness can be imparted to the adhesive layer of the adhesive phosphorescent composite sheet.

  Moreover, it is preferable that the hardness of the said adhesion layer is lower than the hardness of the said base rubber, and the Asker C hardness of the said adhesion layer is 1-60.

  If the Asker C hardness of the adhesive layer is within the above range, an adhesive phosphorescent composite sheet having sufficient adhesiveness and rubber strength is preferable.

  Moreover, it is preferable that the adhesive force with respect to the glass of the said adhesion layer is 0.5-10 N / 25mm.

  Thus, if the adhesive force with respect to the glass of an adhesion layer is a thing within said range, since it becomes an adhesive light storage composite sheet which has rework property and reattachability while having sufficient adhesive force, it is preferable.

  Moreover, it is preferable that the thickness of the said base rubber is 0.05-1 mm, and the thickness of the said adhesion layer is 0.1-2 mm.

  As described above, if the thickness of the base rubber is within the above range, it is advantageous in terms of cost, and an adhesive phosphorescent composite sheet having sufficient elasticity can be obtained. If the thickness of the pressure-sensitive adhesive layer is within the above range, the surface unevenness of the adherend to be attached can be sufficiently absorbed.

  Moreover, it is preferable that the said adhesive light storage composite sheet is what is used for guidance or decoration.

  As described above, the adhesive phosphorescent composite sheet of the present invention is particularly suitable for use as a guide sheet at night or the like, or as a decorative sheet.

  The adhesive phosphorescent composite sheet of the present invention does not have a decrease in adhesive force over a long period of time, and can be reused without being reduced in adhesive strength even when peeled. Furthermore, since it has elasticity, it can follow the surface of expansion and contraction and can provide a sheet with little damage. In addition, the phosphorescent property is higher than that of the conventional phosphorescent pigments, and the afterglow is long, and the high temperature and high humidity resistance is also good. Furthermore, it has good mechanical properties and can provide a high-quality rubber material that can be used effectively in a wide range of fields. Furthermore, since the interfacial affinity between the silicone matrix and the phosphorescent agent is improved by the treatment agent (component (III)), a decrease in luminance is minimized. Moreover, the adhesive light storage composite sheet of the present invention can be suitably used for guidance and decoration at night.

It is sectional drawing which shows an example of the adhesive light storage composite sheet of this invention.

Hereinafter, the present invention will be described in more detail.
As mentioned above, it has flexibility, is excellent in weather resistance and reworkability, can be used without causing a decrease in adhesive strength over a long period of time, and can be re-applied even after peeling, and can be used repeatedly There is a need for an adhesive phosphorescent composite sheet that enables a long period of phosphorescence and that does not cause a decrease in light emission intensity over a long period even under high temperature and high humidity.

As a result of intensive studies to achieve the above object, the present inventors have found that an adhesive phosphorescent composite comprising an adhesive layer made of an adhesive silicone resin or gel laminated on a base rubber in which a phosphorescent agent is dispersed. A sheet,
The base rubber is
(I) Silicone rubber substrate having a JIS-A hardness of 10 to 90 after curing: 100 parts by mass
(II) Luminescent agent: 5-1000 parts by mass,
(III) Alkoxysilane or hydrolyzable methylpolysiloxane or both: It has been found that the above-mentioned problems can be achieved by using an adhesive phosphorescent composite sheet characterized by containing 0.1 to 10 parts by mass. Completed the invention.

  Hereinafter, although the adhesive light storage composite sheet of the present invention will be described in detail, the present invention is not limited thereto.

  Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing an embodiment of the adhesive phosphorescent composite sheet of the present invention. As shown in FIG. 1, the adhesive phosphorescent composite sheet of the present invention is formed by laminating an adhesive layer 2 on one side of a base rubber 1 in which a phosphorescent agent (phosphorescent filler) is dispersed. The cover film 3 is detachably laminated on the top, the cover film 3 is peeled off at the time of use, and the adhesive layer 2 is stuck to a required place.

[Rubber substrate]
Here, as the rubber substrate constituting the base rubber, silicone rubber is used in terms of elasticity, weather resistance, and transparency. The silicone rubber is not particularly limited, and any silicone rubber obtained by curing a conventionally known silicone rubber composition may be used, but a JIS-A hardness measured by a durometer A hardness meter defined in JIS K 6249. 10 to 90 is used. Moreover, it is preferable to use the silicone rubber whose JIS-A hardness is 20-80, especially 25-75 from the point of elasticity and rubber strength. When the JIS-A hardness is less than 10, the strength as rubber may be inferior, and when it exceeds 90, the elasticity may be inferior.

  The silicone rubber composition may be of any curable type, but addition (hydrosilylation) reaction curable type silicone rubber composition or organic peroxide curable type silicone from the point that molding can be done in a short time by heating. Those obtained from the rubber composition are preferred. This addition reaction curable silicone rubber composition may be of a known composition, an alkenyl group-containing organopolysiloxane having two or more alkenyl groups represented by vinyl groups in one molecule, and two or more SiH groups. , Preferably 3 or more organohydrogenpolysiloxanes (usually in an amount such that the molar ratio of SiH groups to alkenyl groups is 0.5 to 4) and platinum group metal-based addition reaction catalysts represented by platinum compounds (Normally, 1 to 1,000 ppm relative to the alkenyl group-containing organopolysiloxane) is used. Further, the organic peroxide curable silicone rubber composition may be of a known composition, preferably an effective amount of organic peroxide as a curing agent in organopolysiloxane having two or more alkenyl groups in one molecule. What is blended (usually 1 to 10 parts by mass with respect to 100 parts by mass of the organopolysiloxane) is used.

  Commercially available products can be used as the silicone rubber composition. For example, as an addition reaction curable silicone rubber composition, KE-1935A / B, KE-1950-60A / B, KEG-2000- manufactured by Shin-Etsu Chemical Co., Ltd. 40A / B and the like are organic peroxide curable silicone rubber compositions such as KE-551-U, KE-571-U, KE-1571-U, and KE-951-U manufactured by Shin-Etsu Chemical Co., Ltd. Used.

[Phosphorescent agent]
The phosphorescent agent (phosphorescent filler) dispersed in the base rubber is not particularly limited, and examples thereof include a zinc sulfide-based phosphorescent agent, a calcium aluminate-based phosphorescent agent, and a strontium aluminate-based phosphorescent agent. It is done.

  Calcium aluminate-based phosphorescent agents and strontium aluminate-based phosphorescent agents have higher afterglow luminance and longer afterglow time than zinc sulfide-based phosphorescent agents. Further, since it is difficult to be decomposed during the molding process, the molding processability is excellent. Further, it does not easily react with moisture contained in the waterproof sheet and Pd stabilizer (additive), and the afterglow characteristics are not deteriorated.

  Calcium aluminate-based phosphorescent agents and strontium aluminate-based phosphorescent agents have a high afterglow luminance and a long afterglow time as described above, and are not decomposed during molding. Since it does not react, it is more suitable as a phosphorescent agent in the present invention. Of these, a strontium aluminate phosphorescent agent having a high afterglow luminance and a long afterglow time is preferably used.

  Examples of the zinc sulfide-based phosphorescent agent include ZnS: Cu (light emitting color: yellow green), ZnS: Cu, Co (light emitting color: yellow green), CaS: Eu, Tm (light emitting color: red), and the like.

As the phosphorescent phosphor filler particularly effectively used for the base rubber phosphorescent layer of the present invention, an aluminate phosphorescent phosphor is used, and in particular, MAl ₂ O ₄ · X _K · Y _L · Z _P [wherein M is one or more metals selected from the group consisting of calcium, barium, strontium, magnesium and mixtures thereof, X is an activator consisting of europium, and Y and Z are groups of lanthanum series elements, respectively. And an activation aid comprising an element selected from the group consisting of manganese, tin and bismuth, K is 0.001 to 10 mol% relative to M, L is 0 to 10 mol% based on M, and P is mol relative to M % Represents 0-10. ] Is preferable.

Examples of phosphorescent phosphors included in the above chemical formula include, for example, europium activated strontium aluminate (SrAl ₂ O ₄ : Eu), europium activated-dysprosium co-activated strontium aluminate (SrAl ₂ O ₄ : Eu, Dy), europium Activation-neodymium co-activated strontium aluminate (SrAl ₂ O ₄ : Eu, Nd), europium activation-praseodymium co-activated strontium aluminate (SrAl ₂ O ₄ : Eu, Pr), europium activation-samarium co-activated strontium aluminate (SrAl ₂ O ₄ : Eu, Sm), europium activated-tin co-activated strontium aluminate (SrAl ₂ O ₄ : Eu, Sn), europium activated-neodymium co-activated calcium aluminate (CaAl ₂ O ₄ : Eu, Nd) Europium activated-samarium co-activated calcium aluminate (CaAl ₂ O ₄ : Eu, Sm), europium activated-thulium co-activated calcium aluminate (CaAl ₂ O ₄ : Eu, Tm), europium activated-neodymium-lanthanum co-activated aluminum Calcium oxide (CaAl ₂ O ₄ : Eu, Nd, La), europium activated-neodymium-gadolinium co-activated calcium aluminate (CaAl ₂ O ₄ : Eu, Nd, Gd), europium activated-neodymium-erbium co-activated calcium aluminate (CaAl ₂ O ₄ : Eu, Nd, Er), europium activated-manganese co-activated calcium aluminate (CaAl ₂ O ₄ : Eu, Mn), europium activated-bismuth co-activated calcium aluminate (CaAl ₂ O ₄ : Eu, Bi), Yu Examples include europium activated-dysprosium-manganese co-activated calcium aluminate (CaAl ₂ O ₄ : Eu, Dy, Mn).

The average particle diameter of the phosphorescent agent (the phosphorescent phosphor etc.) is preferably 0.1 to 70 μm, particularly preferably 0.5 to 60 μm. When the average particle size is 0.1 μm or more, uniform dispersion is facilitated. When the thickness is 70 μm or less, the mechanical properties are not adversely affected. The average particle size can be determined as a cumulative weight average value (D ₅₀₎ in the particle size distribution measurement by laser diffraction method.

  The compounding quantity of a luminous agent is 5-1000 mass parts with respect to 100 mass parts of said silicone rubber base | substrates. When the amount of the phosphorescent agent is less than 5 parts by mass, sufficient afterglow luminance may not be obtained. When it exceeds 1000 parts by mass, it becomes difficult to uniformly disperse the phosphorescent agent in the rubber substrate, and there is a possibility that irregularities of particles are generated on the surface of the adhesive phosphorescent composite sheet.

  The phosphorescent agent is preferably added to the base rubber containing the silicone rubber and the phosphorescent agent so that the amount is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass. If it is 0.5 mass% or more, sufficient afterglow brightness is obtained. On the other hand, if it is 80 mass% or less, a phosphorescent agent will disperse | distribute uniformly and the problem that the unevenness | corrugation of particle | grains generate | occur | produces on the adhesive light storage composite sheet surface does not arise. In addition, the luminance increases in proportion to the added amount. Aluminate phosphorescent phosphors mainly composed of alumina may wear metals and the like. However, if the blending amount is 80% by mass or less, there is no risk of adverse effects such as screw wear of the sheet extruder. .

[Alkoxysilane, hydrolyzable methylpolysiloxane]
In the present invention, the phosphorescent agent is hydrophobized to improve affinity with the rubber substrate, and the phosphorescent agent is dispersed finely as a fine particle in the rubber substrate, and light scattering at the interface between the rubber substrate and the phosphorescent agent is performed. In order to prevent this and improve the high temperature and high humidity resistance, alkoxysilane or hydrolyzable methylpolysiloxane is blended.
The alkoxysilane and hydrolyzable methylpolysiloxane may be used in combination.

As alkoxysilane, the following general formula (1)
R ¹ _a R ² _b Si (OR ³ ) _4-ab (1)
Wherein R ¹ is independently an alkyl group having 6 to 15 carbon atoms, preferably 8 to 14 carbon atoms, and R ² is independently an unsubstituted or substituted carbon atom having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. A monovalent hydrocarbon group, R ³ is independently an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, a is an integer of 1 to 3, preferably 1, and b is 0 to 2 And the sum of a + b is an integer of 1 to 3.)
The alkoxysilane compound represented by these is mentioned.

Examples of R ¹ in the above formula (1) include a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tetradecyl group. When the number of carbon atoms is 6 or more, the affinity between the phosphorescent agent and the rubber substrate can be improved. When it is 15 or less, it does not solidify at room temperature, is easy to handle, and the obtained base rubber has excellent low-temperature characteristics.

Examples of R ² include alkyl groups such as a methyl group, an ethyl group, a propyl group, a hexyl group, and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; an alkenyl group such as a vinyl group and an allyl group; Aryl groups such as phenyl group and tolyl group; aralkyl groups such as 2-phenylethyl group and 2-methyl-2-phenylethyl group; 3,3,3-trifluoropropyl group, 2- (nanofluorobutyl) ethyl group And halogenated hydrocarbon groups such as 2- (heptadecafluorooctyl) ethyl group and p-chlorophenyl group. Among these, a methyl group and an ethyl group are particularly preferable.

Further, the above-mentioned R ^3, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an alkyl group such as hexyl group. Among these, a methyl group and an ethyl group are particularly preferable.

Preferable specific examples of the alkoxysilane compound represented by the above formula (1) include the following. Alkoxysilane can be used alone or in combination of two or more.
C ₆ H ₁₃ Si (OCH ₃ ) ₃
C ₁₀ H ₂₁ Si (OCH ₃ ) ₃
C ₁₂ H ₂₅ Si (OCH ₃ ) ₃
C ₁₂ H ₂₅ Si (OC ₂ H ₅ ) ₃
C ₁₀ H ₂₁ Si (CH ₃ ) (OCH ₃ ) _{2
C 10 H 21 Si (C 6} H 5) (OCH 3) 2
_{C 10 H 21 Si (CH 3} ) (OC 2 H 5) 2
C ₁₀ H ₂₁ Si (CH═CH ₂ ) (OCH ₃ ) _{2
C 10 H 21 Si (CH 2} CH 2 CF 3) (OCH 3) 2

（式中、Ｒ^４は独立に炭素原子数１〜６、好ましくは１〜４のアルキル基であり、ｃは５〜１００、好ましくは１０〜６０の整数である。）
で表される片末端３官能の加水分解性メチルポリシロキサン（分子鎖の片末端がトリアルコキシシリル基で封鎖されたジメチルポリシロキサン）が挙げられる。 As hydrolyzable methylpolysiloxane, the following general formula (2)

(In the formula, R ⁴ is independently an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and c is an integer of 5 to 100, preferably 10 to 60.)
One end trifunctional hydrolyzable methylpolysiloxane represented by the formula (dimethylpolysiloxane in which one end of a molecular chain is blocked with a trialkoxysilyl group).

Specific examples of R ⁴ in the above formula include the same groups as R ³ in the general formula (1). These components can be used alone or in combination of two or more.

  The compounding quantity of alkoxysilane or hydrolyzable methylpolysiloxane or both is 0.1-10 mass parts with respect to 100 mass parts of rubber | gum base | substrates, Preferably it is 0.2-5 mass parts. When the blending amount is less than 0.1 parts by mass, moisture is adsorbed on the surface of the phosphorescent agent under high temperature and high humidity, and the light emission intensity may decrease. When it exceeds 10 parts by mass, the strength, heat resistance, and cold resistance of the obtained base rubber may be lowered.

[Adhesive layer]
The pressure-sensitive adhesive layer is composed of a silicone resin or gel having adhesiveness, and in particular, an addition-curable composition is used in combination with a silicone resin that imparts adhesiveness and a silicone resin that imparts rubber strength. Thus, while having a certain rubber hardness and rubber strength, it is possible to have adhesiveness that can be adhered and fixed to a base material or various parts.

Here, as the adhesive layer,
(A) an organopolysiloxane containing an alkenyl group bonded to an average of at least two silicon atoms in one molecule;
(C) R ′ ₃ SiO _1/2 unit (wherein R ′ is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, R ′ ₃ SiO _1/2 unit and SiO ₂ unit And the molar ratio [R ′ ₃ SiO _1/2 / SiO ₂ ] is 0.5 to 1.5, R ′ contains an alkenyl group, and the total amount thereof is 0.0001 mol / g or more. Coalescence,
(D) an organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule;
(E) It is preferably a cured product of an addition-curable silicone rubber composition containing an addition reaction catalyst, and the cured product preferably has surface tackiness.

Further, the composition further comprises (B) R ₃ SiO _1/2 unit (wherein R is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, and R ₃ SiO _1/2 The molar ratio [R ₃ SiO _1/2 / SiO ₂ ] between the unit and the SiO ₂ unit is 0.5 to 1.5, and R does not contain an alkenyl group or the total amount thereof is 0.0001 mol. Those blended with a resinous copolymer of less than / g can also be suitably used.

[(A) component]
The component (A) of the addition curable silicone rubber composition is an organopolysiloxane having an average of at least two alkenyl groups in one molecule. Examples of the organopolysiloxane of the component (A) include the following: Average composition formula (3)
R ⁵ _d SiO _{(4-d) / 2} (3)
What is shown by can be used.

In the formula, R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group having the same or different carbon number of 1 to 10, preferably 1 to 8, and d is 1.5 to 2.8, preferably 1.8. It is a positive number in the range of ˜2.5, more preferably 1.95 to 2.05. Here, as the unsubstituted or substituted monovalent hydrocarbon group bonded to the silicon atom represented by R ⁵ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, Pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, alkyl group such as decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, phenylpropyl Aralkyl groups such as groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups, octenyl groups and other alkenyl groups, and some or all of the hydrogen atoms of these groups are fluorine. Substituted with halogen atoms such as bromine, chlorine, cyano groups, etc., such as chloromethyl group, chloropro A pill group, a bromoethyl group, a trifluoropropyl group, a cyanoethyl group and the like can be mentioned, but 90 mol% or more of all R ⁵ is preferably a methyl group.

In this case, at least two of R ⁵ must be alkenyl groups (preferably having 2 to 8 carbon atoms, more preferably 2 to 6). The content of the alkenyl group is 0.0001 to 20 mol%, preferably 0.001 to 10 mol%, particularly in the total organic group (that is, the above-mentioned unsubstituted or substituted monovalent hydrocarbon group) R ^5. It is preferable to set it as 0.01-5 mol%. This alkenyl group may be bonded to a silicon atom at the end of the molecular chain, or may be bonded to a silicon atom in the middle of the molecular chain, or may be bonded to both. Those containing bonded alkenyl groups are preferred.

  The degree of polymerization is not particularly limited and can be from liquid to raw rubber at normal temperature. Usually, the average degree of polymerization in terms of polystyrene by gel permeation chromatography (GPC) is 50 to 20,000, preferably 100. Those having a molecular weight of about 10,000 to 10,000, more preferably about 100 to 2,000 are preferably used.

The structure of this organopolysiloxane is basically composed of repeating diorganosiloxane units (R ⁵ ₂ SiO _2/2 ) in the main chain and triorganosiloxy groups (R ⁵ ₃ SiO _1/2 ) at both ends of the molecular chain. ₂ ) or a linear structure blocked with a hydroxydiorganosiloxy group ((HO) R ⁵ ₂ SiO _1/2 ), but may be partially a branched structure, a cyclic structure, or the like.

[Component (B)]
The resinous copolymer of component (B) (that is, a copolymer having a three-dimensional network structure) has R ₃ SiO _1/2 units and SiO ₂ units as main components. Here, R is an unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms. Specific examples of the monovalent hydrocarbon group represented by R include the above ( it can be exemplified the same ones as exemplified for R ⁵ in a) component.

The resinous copolymer of the component (B) may be composed only of the R ₃ SiO _1/2 unit and the SiO ₂ unit, and if necessary, the R ₂ SiO unit or the RSiO _3/2 unit ( R may contain 50% or less, preferably 40% or less, based on the total copolymer mass, with R ₃ SiO _1/2 units, SiO ₂ units, The molar ratio [R ₃ SiO _1/2 / SiO ₂ ] is preferably 0.5 to 1.5, particularly preferably 0.5 to 1.3. If this molar ratio is in the range of 0.5 to 1.5, the tackiness is sufficient. Furthermore, the resinous copolymer of component (B) has an alkenyl group content of less than 0.0001 mol / g (that is, 0 to 0.0001 mol / g), preferably 0.00005 mol / g or less ( That is, it is 0-0.00005 mol / g), and more preferably does not contain an alkenyl group. If the alkenyl group is less than 0.0001 mol / g, it can have sufficient adhesive strength.

  The resinous copolymer of the component (B) may be a liquid that is fluid at room temperature (for example, 25 ° C.) or a solid that is not fluid. Those that are solid at room temperature are preferred. This resinous copolymer can be usually produced by hydrolyzing an appropriate chlorosilane or alkoxysilane by a method well known in the art.

[Component (C)]
The resinous copolymer of component (C) (that is, a copolymer having a three-dimensional network structure) has R ′ ₃ SiO _1/2 units and SiO ₂ units as main components. Here, R ′ is an unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms. Specific examples of the monovalent hydrocarbon group represented by R ′ include it can be exemplified the same ones as exemplified for R ⁵ in component (a).

The resinous copolymer of component (C) may be composed of only the above R ′ ₃ SiO _1/2 unit and SiO ₂ unit, and if necessary, R ′ ₂ SiO unit or R′SiO _{3. / 2} units (R ′ as described above) may be contained in a total amount of 50% or less, preferably 40% or less, based on the total copolymer mass, but R ′ ₃ SiO _1/2 The molar ratio [R ′ ₃ SiO _1/2 / SiO ₂ ] between the unit and the SiO ₂ unit is preferably 0.5 to 1.5, particularly preferably 0.5 to 1.3. If this molar ratio is in the range of 0.5 to 1.5, the tackiness is sufficient. The resinous copolymer (C) preferably has at least two alkenyl groups in one molecule. Furthermore, the resinous copolymer of component (C) has an alkenyl group content of 0.0001 mol / g or more, preferably 0.0001 to 0.003 mol / g, more preferably It is in the range of 0.0002 to 0.002 mol / g. When the alkenyl group content is 0.0001 mol / g or more, sufficient rubber properties can be obtained. When it is 0.003 mol / g or less, the hardness does not become too high, and the adhesive strength does not decrease.

  The resinous copolymer of the component (C) may be a liquid (eg, 10 mPa · s or more, preferably 50 mPa · s or more) that has fluidity at room temperature (25 ° C.), or a solid that has no fluidity. It may be. This resinous copolymer can be usually produced by hydrolyzing an appropriate chlorosilane or alkoxysilane by a method well known in the art.

  In addition, when mix | blending (B) component, as content of the alkenyl group in the sum total of the resinous copolymer of (B) component, and the resinous copolymer of (C) component, rubber physical property and adhesiveness are included. From the above points, it is preferably 0.00001 to 0.002 mol / g, particularly preferably 0.00005 to 0.001 mol / g.

  Here, the compounding amount of the component (A) is 10 to 75 parts by mass, particularly 20 to 70 parts by mass, and the compounding amount of the component (C) is 5 to 50 parts by mass, particularly 10 to 40 parts by mass. (A) When the compounding quantity of a component is 10 mass parts or more, it has sufficient rubber elasticity. In the case of 75 parts by mass or less, adhesiveness and strength are sufficient. When the blending amount of the component (C) is 5 parts by mass or more, sufficient tackiness is obtained, and when it is 50 parts by mass or less, the tackiness and rubber physical properties are sufficient.

  The component (B) may not be blended, but more sufficient tackiness can be imparted by blending the resinous copolymer substantially free of alkenyl groups of the component (B). . Therefore, although the compounding quantity of (B) component is 0-70 mass parts at this point, when mix | blending, it is preferable that it is 20-70 mass parts, especially 25-60 mass parts. (B) When the compounding quantity of a component is 70 mass parts or less, adhesiveness and rubber physical property will become sufficient. In addition, the sum total of (A), (B), (C) component is 100 mass parts.

[(D) component]
The component (D) is an organohydrogenpolysiloxane having at least 2, preferably 3 or more hydrogen atoms (SiH groups) bonded to a silicon atom in one molecule, and the SiH group in the molecule is the above (A). The alkenyl group bonded to the silicon atom in the component, the component (B) and the component (C) is cross-linked by a hydrosilylation addition reaction, and acts as a curing agent for curing the composition.

The organohydrogenpolysiloxane of component (D) includes the following average composition formula (4)
R ⁶ _e H _f SiO _{(4-ef) / 2} (4)
(In the formula, R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, e is 0.7 to 2.1, f is 0.001 to 1.0, and e + f is a positive number satisfying 0.8 to 3.0.)
And those having at least 2 (usually 2 to 200), preferably 3 to 100, more preferably 3 to 50 silicon atom-bonded hydrogen atoms in one molecule are suitably used.

Here, examples of the monovalent hydrocarbon group for R ⁶ include the same groups as those exemplified for R ⁵ , but those having no aliphatic unsaturated group are preferable. Further, e is preferably 0.8 to 2.0, f is preferably 0.01 to 1.0, e + f is preferably 1.0 to 2.5, and the molecular structure of the organohydrogenpolysiloxane is: The structure may be any of linear, cyclic, branched, and three-dimensional network. In this case, the number of silicon atoms in one molecule (or the degree of polymerization) is preferably 2 to 300, particularly about 4 to 150 at room temperature (25 ° C.). In addition, the hydrogen atom couple | bonded with a silicon atom may be located in any of the molecular chain terminal and the middle of a molecular chain, and may be located in both.

Examples of the organohydrogenpolysiloxane of component (D) include trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer at both ends, and dimethylhydrogensiloxy groups at both ends. Blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy group blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group blocked methylhydrogen diphenylsiloxane-dimethylsiloxane _copolymers, copolymers consisting of _(CH 3) 2 _{HSiO 1/2} units and _{SiO 4/2} units, (C _{3) 2} HSiO _1/2 units and the _{SiO 4/2} units _{(C 6} H _5), such as copolymers comprising _{SiO 3/2} units and the like.

  The blending amount of the organohydrogenpolysiloxane of the component (D) is 0.5 to 30 parts by mass, particularly 0.8 to 20 parts per 100 parts by mass in total of the components (A), (B) and (C). Part by mass. If the amount is 0.5 to 30 parts by mass, sufficient rubber strength can be obtained. The organohydrogenpolysiloxane of component (D) is bonded to the silicon atom in component (D) relative to the alkenyl group bonded to the silicon atom included in components (A), (B), and (C). The amount of hydrogen atoms (SiH groups) is blended in such an amount that the molar ratio is 0.32 to 0.75.

[(E) component]
As an addition reaction catalyst for component (E), platinum black, platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, chloroplatinic acid and vinyl Examples include complexes with siloxanes, platinum-based catalysts such as platinum bisacetoacetate, palladium-based catalysts, and rhodium-based catalysts. In addition, the addition amount of this addition reaction catalyst can be made into a catalyst amount, and 0.5-1,000 ppm with respect to the total amount of (A), (B), (C) component as a platinum group metal normally, It is about 1 to 500 ppm.

  The hardness of the adhesive layer is smaller than the hardness of the base rubber. When the component (B) is included, the Asker C hardness is preferably in the range of 1-60, more preferably in the range of 2-55. When Asker C hardness is 1 or more, the strength as rubber is excellent. In the case of 60 or less, the adhesiveness is sufficient. When the component (B) is not included, the penetration (based on the consistency test method) based on JIS K2220 is preferably in the range of 1 to 100, more preferably 5 to 90. When the penetration is 1 or more, the adhesiveness is sufficient. When it is 100 or less, sufficient rubber strength can be obtained.

  Moreover, based on JISZ0237, it adheres to glass (Nippon Sheet Glass Co., Ltd., FL2.0), and the adhesive force when a 180 degree peel test is performed at a peeling speed of 300 mm / min is 0.5 to 10 N / 25 mm. In particular, 0.7 to 8 N / 25 mm is preferable. In the case of 0.5 N / 25 mm or more, when the adhesive layer is adhered to a desired adherend part, the adhesive force with respect to the adherend part is sufficient, so that there is no problem in adhering. In the case of 10N / 25mm or less, it is excellent in rework property and reattachability.

[Other ingredients]
In addition to the above-described components, the composition for forming the base rubber layer and the adhesive layer includes, as necessary, other components such as fumed silica, precipitated silica, quartz powder, diatomaceous earth, and calcium carbonate. In addition, a filler such as carbon black, conductive zinc white, conductive powder such as metal powder, and heat-resistant agent such as iron oxide and cerium oxide may be blended. Furthermore, hydrosilylation reaction control agents such as nitrogen-containing compounds, acetylene compounds, phosphorus compounds, nitrile compounds, carboxylates, tin compounds, mercury compounds, sulfur compounds, internal mold release agents such as dimethyl silicone oil, adhesion imparting agents, thixotropes It is optional to add a property-imparting agent or the like.

  The thickness of the base rubber is 0.05 to 1 mm, preferably 0.1 to 0.7 mm. When the thickness of the base rubber is 0.05 mm or more, the base rubber can have sufficient elasticity. In the case of 1 mm or less, the weight does not become too high and does not affect the pasting. Moreover, it is advantageous also in cost. On the other hand, the thickness of the adhesive layer is preferably in the range of 0.1 to 2 mm, more preferably in the range of 0.15 to 1.5 mm. When the thickness of the pressure-sensitive adhesive layer is 0.1 mm or more, the pressure-sensitive adhesive layer can absorb surface irregularities of the adherend portion to be attached. In the case of 2 mm or less, the rubber strength of the affixed surface does not depend on the adhesive layer, and there is no possibility of causing rubber breakage.

[Method for producing adhesive phosphorescent composite sheet]
When forming the adhesive light-storing composite sheet of the present invention, first, a base rubber is formed. In this case, the base rubber may be formed as a single layer using a rubber composition such as a silicone rubber composition, or may be formed as a composite layer with metal or various resins, for example, compression molding or injection molding. Integrate with other base materials by directly obtaining a sheet by injection molding, by molding a sheet on a metal substrate, resin substrate, resin film by insert molding, or by dipping, coating, calendar molding, screen printing, etc. For example, there is a method of obtaining a rubber sheet. In this case, calendar molding is preferable because it can be suitably used.

  The adhesive layer may be formed after the adhesive layer is laminated on the base rubber or after the composition forming the base rubber is cured to form the base rubber. The composition to be formed is preferably calendered on a film of polyethylene terephthalate (PET) or the like and separated, and a composition that forms an adhesive layer in an unvulcanized state is preferably laminated.

  Examples of a method for obtaining a laminated sheet include a method in which a composition for forming an adhesive layer is dipped, coated, screen-printed or the like on a composition for forming a base rubber layer. In particular, a method of coating molding is preferable. By simultaneously curing the base rubber composition and the adhesive layer composition, the adhesion at the lamination interface can be obtained. In addition, as these hardening conditions, it is preferable to set it as the range for 10 second-1 hour at 80-250 degreeC. Further, after-curing may be performed at 120 to 250 ° C. for about 1 to 100 hours for the purpose of removing low molecular siloxane.

  The pressure-sensitive phosphorescent composite sheet of the present invention can be used as a guide sheet at night or as a decorative sheet. Specifically, human bodies such as badges, emblems, seals, covers, earrings, piercings, character sheets, nail polish, nail sheets, sun protection sheets, protective sheets, elastic sheets, cheering face or arm seals (national flags, teams, etc.) As decorative paste sheets, decorative items such as toys, bracelets, necklaces, pendants, brooches, hair ornaments, tie ornaments, etc. Houseware parts such as glass windows, baths, sinks, handrails, door knobs, TVs, telephones, air conditioner indoor units, personal computers, cameras, video cameras, photocopiers, washing machines, dehumidifiers, electric kettles, vacuum cleaners, lighting fixtures, etc. Automotive and electronic parts such as dashboards, handles, levers, etc. Over the handrail can be used as such as a part or the whole of the cover member of the train and bus hoisting ring-grip bar and their members.

  In addition, as shown in FIG. 1, the composite sheet of the present invention usually has a cover film 3 such as a polyethylene terephthalate (PET) sheet laminated on the adhesive layer 2 so that the cover film 3 can be peeled off. It removes and the adhesion layer 2 is stuck on the required to-be-adhered part. In this case, if necessary, the composite sheet of the present invention can be peeled off from the adherend and reattached. Thus, the composite sheet of this invention is excellent in reworkability.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, “part” means “part by mass” and “%” means “% by mass”.

[Example 1]
(Base rubber layer)
As a transparent uncrosslinked dimethylsilicone rubber compound, millable dimethylsilicone rubber compound KE-571-U (manufactured by Shin-Etsu Chemical Co., Ltd., based on vinyl group-containing dimethylpolysiloxane having a polymerization degree of about 5,000, 40% or less of dry silica having a specific surface area of 200 m ² / g by BET method, 10% or less of silanol group-blocked dimethylsiloxane oligomer (silica dispersant) having a molecular weight of 700 or less, and a phenyl group in the compound. 1 part of alkoxysilane C ₁₂ H ₂₅ Si (OC ₂ H ₅ ) ₃ represented by the following formula is added to 100 parts, and aluminate phosphorescent filler “GLL-300FF” (trade name, fundamental special) Chemical Co., Ltd.) 10 parts, addition (hydrosilylation) reaction vulcanizing agent C-25A / B (Shin-Etsu Chemical ( )) Was added in 0.5 / 2.0 parts each and kneaded with two rolls by calendering and unvulcanized with a thickness of 0.3 mm on 100 μm embossed PET. Thus, a compound composition was obtained so as to obtain a sheet.

(Adhesive layer)
40 parts of dimethylpolysiloxane (1) having an average degree of polymerization of 300 with both ends of the molecular chain blocked with dimethylvinylsiloxy groups, (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ solid at room temperature (25 ° C.) Resinous copolymer consisting of units (2) [(CH ₃ ) ₃ SiO _1/2 units / SiO ₂ units = 0.75 (molar ratio)] 45 parts, (CH ₃ ) ₃ SiO _{1 / two units, CH 2 = CH (CH 3} ) 2 SiO 1/2 units and of SiO ₂ units resinous copolymer _{(3) [((CH 3} ) 3 SiO 1/2 units ₊ CH 2 = CH (CH ₃ ) ₂ SiO _1/2 unit) / SiO ₂ unit = 0.8 (molar ratio), vinyl group content = 0.0005 mol / g] 15 parts were mixed at 150 ° C. for 3 hours and then cooled to obtain a silicone rubber base. Obtained. A dimethylsiloxane / methylhydrogensiloxane copolymer (4) (degree of polymerization 20, SiH) having 100 parts of this silicone rubber base, both ends of the molecular chain blocked with trimethylsiloxy groups as crosslinking agents, and having SiH groups on the molecular side chains. 1.39 parts of a base amount of 0.0060 mol / g) and 0.05 parts of ethynylcyclohexanol as a reaction control agent were added, and stirring was continued for 15 minutes to obtain a silicone rubber composition. This silicone rubber composition was mixed with 0.1 part of a platinum catalyst (Pt concentration 1%) to obtain a pressure-sensitive adhesive composition.

  On the unvulcanized base rubber composition, using a comma coater, the pressure-sensitive adhesive composition is laminated and coated to a thickness of 0.5 mm, and then heated and cured in a heating furnace at 150 ° C. for 10 minutes to form two layers. A laminated cured sheet was obtained. In addition, the hardness of the silicone rubber base | substrate which has not mix | blended the luminous agent was JIS-A hardness 65, and the hardness of the adhesion layer was Asker C hardness 40.

Table 1 shows the results obtained by peeling the substrate-side PET from the obtained laminated sheet and evaluating it by the following methods.
As a product, the PET attached to the base rubber layer side is peeled off, and a glossy 75 μm PET is attached to the adhesive layer side as shown in FIG.

２部を加え、さらにアルミン酸塩蓄光性フィラー「Ｇ−３００Ｍ」（商品名、根本特殊化学（株）製）１０部、付加（ヒドロシリル化）反応系加硫剤Ｃ−２５Ａ／Ｂ（信越化学工業（株）製）をそれぞれ０．５／２．０部添加して二本ロールで混練したジメチルシリコーンゴム組成物をカレンダー成形にて、１００μｍのシボ付のＰＥＴ上に厚さ０．２ｍｍの未加硫のシートが得られるよう分だししたコンパウンド組成物を得た。 [Example 2]
(Base rubber layer)
Millable dimethyl silicone rubber compound KE-571-U (manufactured by Shin-Etsu Chemical Co., Ltd., a vinyl group-containing dimethylpolysiloxane having a polymerization degree of about 5,000 as a main component as a transparent uncrosslinked dimethyl silicone rubber compound, BET 40% or less of dry silica having a specific surface area of 200 m ² / g according to the method, 10% or less of both-end silanol group-blocked dimethylsiloxane oligomer (silica dispersant) having a molecular weight of 700 or less, and a phenyl group in the compound. 100 parts) hydrolyzable methylpolysiloxane represented by the following formula (5)

2 parts are added, 10 parts of aluminate phosphorescent filler “G-300M” (trade name, manufactured by Nemoto Special Chemical Co., Ltd.), addition (hydrosilylation) reaction system vulcanizing agent C-25A / B (Shin-Etsu Chemical) A dimethyl silicone rubber composition kneaded with two rolls by adding 0.5 / 2.0 parts each of Kogyo Kogyo Co., Ltd.) was formed into a 0.2 mm thickness on 100 μm embossed PET by calendering. A compound composition was obtained so as to obtain an unvulcanized sheet.

(Adhesive layer)
The adhesive layer was the same as in Example 1, and a two-layer laminated cured sheet was obtained in the same manner as in Example 1. In addition, the hardness of the silicone rubber base | substrate which has not mix | blended the luminous agent was JIS-A hardness 60, and the hardness of the adhesion layer was Asker C hardness 40.
Table 1 shows the results obtained by peeling the substrate-side PET from the obtained laminated sheet and evaluating it by the following methods.

[Example 3]
A two-layer cured sheet was prepared in the same manner as in Example 1 except that the aluminate phosphorescent filler of the base rubber layer was 10 parts “GLL-300M” (trade name, manufactured by Nemoto Special Chemical Co., Ltd.). Obtained.
Table 1 shows the results obtained by peeling the substrate-side PET from the obtained laminated sheet and evaluating it by the following methods.

[Example 4]
(Base rubber layer)
The base rubber layer was the same as in Example 1 except that 30 parts of the aluminate phosphorescent filler was used.

(Adhesive layer)
75 parts of dimethylpolysiloxane (1) whose molecular chain both ends are blocked with dimethylvinylsiloxy groups and whose average degree of polymerization is 1,000, (CH ₃ ) ₃ SiO _1/2 unit, CH ₂ ═CH solid at room temperature _{(CH 3)} 2 _{SiO 1/2} units and of SiO ₂ units resinous copolymer _{(3) [((CH 3} ) 3 SiO 1/2 units ₊ CH ₂ = _CH (CH 3) _{2 SiO 1/2} units ) / SiO ₂ unit = 0.8 (molar ratio), vinyl group content = 0.0005 mol / g] 25 parts were mixed at 150 ° C. for 3 hours and then cooled to obtain a silicone rubber base. A dimethylsiloxane / methylhydrogensiloxane copolymer (4) (degree of polymerization 20, SiH) having 100 parts of this silicone rubber base, both ends of the molecular chain blocked with trimethylsiloxy groups as crosslinking agents, and having SiH groups on the molecular side chains. 1.39 parts of a base amount of 0.0060 mol / g) and 0.05 parts of ethynylcyclohexanol as a reaction control agent were added, and stirring was continued for 15 minutes to obtain a silicone rubber composition. This silicone rubber composition was mixed with 0.1 part of a platinum catalyst (Pt concentration 1%) to obtain a pressure-sensitive adhesive composition. Others were obtained in the same manner as in Example 1 to obtain a two-layer laminated cured sheet. The penetration of the adhesive layer based on JIS K2220 was 51.
Table 1 shows the results obtained by peeling the substrate-side PET from the obtained laminated sheet and evaluating it by the following methods.

[Example 5]
A two-layer laminated cured sheet was obtained in the same manner as in Example 4 except that 30 parts of the aluminate phosphorescent filler of the base rubber layer was used in Example 2.
Table 1 shows the results obtained by peeling the substrate-side PET from the obtained laminated sheet and evaluating it by the following methods.

１．５部を加え、さらにアルミン酸塩蓄光性フィラー「ＧＬＬ−３００ＦＦ」（商品名、根本特殊化学（株）製）３０部、付加（ヒドロシリル化）反応系加硫剤Ｃ−２５Ａ／Ｂ（信越化学工業（株）製）をそれぞれ０．５／２．０部添加して二本ロールで混練したジメチルシリコーンゴム組成物をカレンダー成形にて、１００μｍのシボ付のＰＥＴ上に厚さ０．３ｍｍの未加硫のシートが得られるよう分だししたコンパウンド組成物を得た。 [Example 6]
(Base rubber layer)
As a transparent uncrosslinked dimethylsilicone rubber compound, millable dimethylsilicone rubber compound KE-571-U (manufactured by Shin-Etsu Chemical Co., Ltd., based on vinyl group-containing dimethylpolysiloxane having a polymerization degree of about 5,000, 40% or less of dry silica having a specific surface area of 200 m ² / g by BET method, 10% or less of silanol group-blocked dimethylsiloxane oligomer (silica dispersant) having a molecular weight of 700 or less, and a phenyl group in the compound. Not 100)
0.5 part of alkoxysilane C ₁₂ H ₂₅ Si (OC ₂ H ₅ ) ₃ and hydrolyzable methylpolysiloxane represented by the following formula (5)

1.5 parts are added, 30 parts of aluminate phosphorescent filler “GLL-300FF” (trade name, manufactured by Nemoto Special Chemical Co., Ltd.), addition (hydrosilylation) reaction system vulcanizing agent C-25A / B ( A dimethyl silicone rubber composition obtained by adding 0.5 / 2.0 parts of Shin-Etsu Chemical Co., Ltd. and kneading with two rolls was formed on a 100 μm embossed PET with a thickness of 0. A compound composition was obtained so that a 3 mm unvulcanized sheet was obtained.

(Adhesive layer)
40 parts of dimethylpolysiloxane (1) having an average degree of polymerization of 300 with both ends of the molecular chain blocked with dimethylvinylsiloxy groups, (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ solid at room temperature (25 ° C.) Resinous copolymer consisting of units (2) [(CH ₃ ) ₃ SiO _1/2 units / SiO ₂ units = 0.75 (molar ratio)] 45 parts, (CH ₃ ) ₃ SiO _{1 / 2 units, CH 2 = CH (CH 3} ) 2 SiO 1/2 units and of SiO ₂ units resinous copolymer _{(3) [((CH 3} ) 3 SiO 1/2 units ₊ CH 2 = CH (CH ₃ ) ₂ SiO _1/2 unit) / SiO ₂ unit = 0.8 (molar ratio), vinyl group content = 0.0005 mol / g] 15 parts were mixed at 150 ° C. for 3 hours and then cooled to obtain a silicone rubber base. Obtained. A dimethylsiloxane / methylhydrogensiloxane copolymer (4) (degree of polymerization 20, SiH) having 100 parts of this silicone rubber base, both ends of the molecular chain blocked with trimethylsiloxy groups as crosslinking agents, and having SiH groups on the molecular side chains. 1.39 parts of a base amount of 0.0060 mol / g) and 0.05 parts of ethynylcyclohexanol as a reaction control agent were added, and stirring was continued for 15 minutes to obtain a silicone rubber composition. This silicone rubber composition was mixed with 0.1 part of a platinum catalyst (Pt concentration 1%) to obtain a pressure-sensitive adhesive composition.

  On the unvulcanized base rubber composition, using a comma coater, the pressure-sensitive adhesive composition is laminated and coated to a thickness of 0.5 mm, and then heated and cured in a heating furnace at 150 ° C. for 10 minutes to form two layers. A laminated cured sheet was obtained.

  Table 1 shows the results obtained by peeling the substrate-side PET from the obtained laminated sheet and evaluating it by the following methods.

[Comparative Example 1]
A two-layer laminated cured sheet was obtained in the same manner as in Example 1 except that no alkoxysilane was added to the base rubber layer.
Table 1 shows the results obtained by peeling the substrate-side PET from the obtained laminated sheet and evaluating it by the following methods.

[Comparative Example 2]
A two-layer laminated cured sheet was obtained in the same manner as in Example 2 except that hydrolyzable methylpolysiloxane was not added to the base rubber layer.
Table 1 shows the results obtained by peeling the substrate-side PET from the obtained laminated sheet and evaluating it by the following methods.

[Evaluation items]
・ Adhesiveness The obtained sheet was cut into a width of 25 mm and a length of 10 cm, and glass FL2.0 manufactured by Nippon Sheet Glass Co., Ltd. was degreased with alcohol in accordance with JIS Z 0237, and then air-dried on a sheet of 4 mm thick glass. The adhesive layer side of was attached, the glass and the adhesive layer were peeled off at 180 ° peel at a rate of 300 mm / min at room temperature, and the adhesive strength was measured.

・ Long-term sticking stability The above-prepared adhesive sheet is cut to a width of 25 mm and a length of 10 cm on a 4 mm thick glass substrate, the adhesive layer side is attached, and room temperature is 1 month at a humidity of 50% RH. After storage, the glass and the adhesive layer were peeled off at 180 ° peel at a rate of 300 mm / min at room temperature, and the adhesive strength was measured.

-Re-peelability On the 4 mm-thick glass substrate, the prepared adhesive sheet was cut to a width of 25 mm and a length of 10 cm, the adhesive layer side was attached, and stored for 1 month at room temperature and 50% RH humidity. Thereafter, the glass and the adhesive layer were peeled off at 180 ° peel at a rate of 300 mm / min at room temperature, and it was confirmed whether or not the adhesive component was transferred to the glass surface. Those where the adhesive component migrated were marked with ×, and those which did not migrate were marked with ○.

-Re-adhesiveness On the 4 mm-thick glass substrate, the prepared adhesive sheet is cut to a width of 25 mm and a length of 10 cm, the adhesive layer side is attached, peeled off, and then applied again to another glass substrate. The glass and the adhesive layer were peeled off at 180 ° peel at a rate of 300 mm / min at room temperature, and the adhesive strength was measured.

-Elasticity against deformation When the laminated film (laminated sheet) was bent at 180 °, the presence or absence of damage to the laminated sheet was confirmed. Those with no change were marked with ○, and those with cracks / deformation were marked with ×.

-Human body skin adhesion retention The sheet | seat was cut into 3 cm x 2 cm, the adhesion layer side was stuck on human skin, and the adhesion state after one day was confirmed. Those that were not peeled were marked with ◯, and those that were peeled off were marked with ×.

-Human body nail adhesion retention The sheet was cut so that it could be affixed to a human nail, the adhesive layer side was attached, and the adhesion state after one day was confirmed. Those that were not peeled were marked with ◯, and those that were peeled off were marked with ×.

· After irradiating for 20 minutes at an illuminance of 200lx with afterglow luminance conventional light source _{D 65,} luminance meter afterglow luminance after lapse of 20 minutes (Konica Minolta Corporation, trade name, LS-100) was measured by.

-Afterglow time After irradiation for 20 minutes at an illuminance of 200 lx using the ordinary light source D ₆₅ , the time for which the afterglow luminance was attenuated to 0.32 mcd / m ² was measured.

-High temperature and high humidity resistance A value of 80% or more of the afterglow luminance when aged for 1000 hours with a high temperature and high humidity machine of 85 ° C / 85% RH is ◯, and a value of less than 80% is x.

  As shown in Table 1, the adhesive phosphorescent composite sheets (Examples 1 to 6) that satisfy the requirements of the present invention have flexibility, excellent weather resistance and reworkability, and have adhesive strength over a long period of time. Can be used without degrading, and can be re-applied even after peeling, enabling repeated use, long phosphorescence time, and long-term emission intensity does not decrease even at high temperatures and high humidity It turns out that it is a thing. On the other hand, in Comparative Examples 1 and 2 in which the base rubber does not contain the component (III) (alkoxysilane, hydrolyzable methylpolysiloxane), the high temperature and high humidity resistance deteriorated.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  DESCRIPTION OF SYMBOLS 1 ... Base rubber, 2 ... Adhesive layer, 3 ... Cover film.

Claims (11)

An adhesive phosphorescent composite sheet in which an adhesive layer made of an adhesive silicone resin or gel is laminated on a base rubber in which a phosphorescent agent is dispersed,
The base rubber is
(I) Silicone rubber substrate having a JIS-A hardness of 10 to 90 after curing: 100 parts by mass
(II) Luminescent agent: 5-1000 parts by mass,
(III) Adhesive phosphorescent composite sheet characterized in that it contains 0.1 to 10 parts by mass of alkoxysilane or hydrolyzable methylpolysiloxane or both. The alkoxysilane in the component (III) is represented by the following general formula (1)
R ¹ _a R ² _b Si (OR ³ ) _4-ab (1)
(Wherein R ¹ is an alkyl group having 6 to 15 carbon atoms, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ³ is an alkyl group having 1 to 6 carbon atoms, and a is An integer of 1 to 3, b is an integer of 0 to 2, and a + b is an integer of 1 to 3.)
It is represented by these, The adhesive light storage composite sheet of Claim 1 characterized by the above-mentioned. The hydrolyzable methylpolysiloxane in the component (III) is represented by the following general formula (2)

(In the formula, R ⁴ is an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100.)
The pressure-sensitive phosphorescent composite sheet according to claim 1 or 2, wherein the one-terminal trifunctional hydrolyzable methylpolysiloxane represented by formula (1) is used. The phosphorescent agent is represented by the general formula: MAl ₂ O ₄ · X _K · Y _L · Z _P [wherein M is one or more metals selected from the group consisting of calcium, barium, strontium, magnesium and mixtures thereof, X is an activator comprising europium, Y and Z are each an activation aid comprising an element selected from the group of lanthanum elements and a group consisting of manganese, tin and bismuth, and K is 0.001 to 0.001 mol% relative to M. 10, L represents 0 to 10 in mol% based on M, and P represents 0 to 10 in mol% based on M. 4. The phosphor according to claim 1, wherein the phosphor has an average particle size of 0.1 to 70 μm. 5. Adhesive phosphorescent composite sheet. The adhesive layer is (A) an organopolysiloxane containing an alkenyl group bonded to an average of at least two silicon atoms in one molecule: 10 to 75 parts by mass,
(C) R ′ ₃ SiO _1/2 unit (wherein R ′ is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, R ′ ₃ SiO _1/2 unit and SiO ₂ unit And the molar ratio [R ′ ₃ SiO _1/2 / SiO ₂ ] is 0.5 to 1.5, R ′ contains an alkenyl group, and the total amount thereof is 0.0001 mol / g or more. Combined: 5-50 parts by mass,
(D) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule: 0.5 to 30 mass with respect to 100 mass parts in total of the component (A) and the component (C) And the amount of hydrogen atoms bonded to silicon atoms in component (D) relative to alkenyl groups bonded to silicon atoms contained in components (A) and (C) is 0.32 in molar ratio. An amount of ~ 0.75,
(E) Addition reaction catalyst: It consists of a cured product of an addition-curable silicone rubber composition containing a catalytic amount, and the cured product has surface adhesiveness. Item 5. The adhesive phosphorescent composite sheet according to any one of items 4.   The hardness of the said adhesion layer is lower than the hardness of the said base rubber, and the penetration degree prescribed | regulated to JISK2220 of the said adhesion layer is 1-100, Any of the Claims 1-5 characterized by the above-mentioned. 2. The adhesive phosphorescent composite sheet according to item 1. The adhesive layer is (A) an organopolysiloxane containing an alkenyl group bonded to an average of at least two silicon atoms in one molecule: 10 to 75 parts by mass,
(B) R ₃ SiO _1/2 unit (wherein R is an unsubstituted or substituted monovalent hydrocarbon group) and a SiO ₂ unit as main components, and the moles of R ₃ SiO _1/2 unit and SiO ₂ unit A resin material having a ratio [R ₃ SiO _1/2 / SiO ₂ ] of 0.5 to 1.5 and R does not contain an alkenyl group or the total amount is less than 0.0001 mol / g. Polymer: 20 to 70 parts by mass,
(C) R ′ ₃ SiO _1/2 unit (wherein R ′ is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, R ′ ₃ SiO _1/2 unit and SiO ₂ unit And the molar ratio [R ′ ₃ SiO _1/2 / SiO ₂ ] is 0.5 to 1.5, R ′ contains an alkenyl group, and the total amount thereof is 0.0001 mol / g or more. Combined: 5-50 parts by mass,
(D) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule: 100 parts by mass in total of the component (A), the component (B), and the component (C) And 0.5 to 30 parts by mass of the silicon atom in the component (D) with respect to the alkenyl group bonded to the silicon atom contained in the component (A), the component (B), and the component (C). The amount of hydrogen atoms bonded to is such that the molar ratio is 0.32-0.75,
(E) Addition reaction catalyst: It consists of a cured product of an addition-curable silicone rubber composition containing a catalytic amount, and the cured product has surface adhesiveness. Item 5. The adhesive phosphorescent composite sheet according to any one of items 4.   The hardness of the said adhesion layer is lower than the hardness of the said base rubber, The Asker C hardness of the said adhesion layer is 1-60, The any one of the Claims 1 to 4 characterized by the above-mentioned. The adhesive phosphorescent composite sheet according to Item.   The adhesive phosphorescent composite sheet according to any one of claims 1 to 8, wherein the adhesive force of the adhesive layer to glass is 0.5 to 10 N / 25 mm.   The thickness of the said base rubber is 0.05-1 mm, The thickness of the said adhesion layer is 0.1-2 mm, It is any one of Claims 1-9 characterized by the above-mentioned. Adhesive phosphorescent composite sheet.   The adhesive light storage composite sheet according to any one of claims 1 to 10, wherein the adhesive light storage composite sheet is used for guidance or decoration.

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