JP7127964B2 - Mechanoluminescent resin composition and method for increasing the mechanoluminescent intensity of the mechanoluminescent resin composition - Google Patents

Description

The present invention relates to a mechanoluminescent resin composition and a method for increasing the mechanoluminescent intensity of the mechanoluminescent resin composition.

A luminescent material is known that emits visible light at around room temperature when a substance is given an external stimulus. Among them, a material that emits light upon being mechanically stimulated by an externally applied force (compression, displacement, friction, impact, etc.) is called a mechanoluminescent material.

As an application of such a mechanoluminescent material, by applying a composition containing a mechanoluminescent material to a concrete structure, abnormal deformations and cracks occurring in the concrete structure can be sensed, and destruction of the concrete structure can be prevented. It is proposed to use it to prevent damage from occurring (see Patent Literature 1).

Also, as a method for improving the luminescence intensity of a mechanoluminescent material, a technique of blending particles with a higher elastic modulus than the bonding material containing the mechanoluminescent material has been proposed (see Patent Document 2).

JP 2013-155062 A JP 2007-055144 A

In the application proposed in Patent Document 1, if the mechanoluminescent material can emit light even when the stress applied to the structure is small, it becomes possible to detect an abnormality occurring in the structure at an early stage. This is particularly effective in preventing destruction of objects. Therefore, improvement for increasing the luminescence intensity of the mechanoluminescent material has been particularly demanded, but the technique described in Patent Document 2 is insufficient to increase the luminescence intensity, and the mechanoluminescent intensity cannot be improved. A technique that can be further improved has been demanded.

In order to improve the mechanoluminescent intensity of the composition containing the mechanoluminescent material, it is effective to increase the content of the mechanoluminescent material.
However, the mechanoluminescent material is made of relatively expensive materials, and when it is used in a paint or the like, it is necessary to apply the composition over a wide area. It is desired not to increase it excessively.

In view of such circumstances, an object of the present invention is to provide a stress-stimulated luminescent resin composition having a higher stress-stimulated luminescent intensity without excessively increasing the content of the stress-stimulated luminescent material.

The present inventors added an inorganic compound to the stress-stimulated luminescent material, and further determined the average particle size and refractive index of the inorganic compound to be within a predetermined range, thereby achieving stress without excessively increasing the content of the stress-stimulated luminescent material. The present inventors have found that the emission intensity can be increased, and arrived at the present invention.

That is, the mechanoluminescent resin composition of the present invention is
A stress-stimulated luminescent resin composition containing a stress-stimulated luminescent material, an inorganic compound, and a synthetic resin,
The average particle size of the mechanoluminescent material is larger than the average particle size of the inorganic compound,
The inorganic compound has a refractive index of 1.35 to 1.90.

The mechanoluminescent material emits light when particles of the mechanoluminescent material come into contact with other particles. The particles of the other party with which the particles of the mechanoluminescent material that emit light come into contact may be the particles of the mechanoluminescent material, or may be particles other than the mechanoluminescent material. Among them, when the amount of the mechanoluminescent material is fixed, the emission intensity can be improved by adding the above-mentioned predetermined inorganic compound, which is inexpensive. Luminescence of moderate intensity can be produced.

The inventors of the present invention have found that when blending an inorganic compound, blending an inorganic compound having an average particle size smaller than that of the mechanoluminescent material is effective for obtaining a large mechanoluminescent intensity. . Therefore, in the stress-stimulated luminescent resin composition of the present invention, the average particle size of the stress-stimulated luminescent material is larger than the average particle size of the inorganic compound.
Furthermore, if the inorganic compound is a material that inhibits light, the intensity of the light that can be extracted is reduced, making it impossible to obtain a strong mechanoluminescent intensity. It has established. When the refractive index of the inorganic compound is 1.90 or less, a large mechanoluminescent intensity can be obtained without preventing the light emitted from the mechanoluminescent material from exiting the mechanoluminescent resin composition. Moreover, it is difficult to think of a practically usable inorganic compound having a refractive index of less than 1.35.

In the stress-stimulated luminescent resin composition of the present invention, the total amount of the stress-stimulated luminescent material and the inorganic compound contained in the stress-stimulated luminescent resin composition is 250 parts by weight or more based on 100 parts by weight of the synthetic resin. and the weight ratio of the stress-stimulated luminescent material to the inorganic compound is preferably 2/1 to 9/1.

The lower limit of the total amount of the mechanoluminescent material and the inorganic compound contained in the mechanoluminescent resin composition, which is necessary to obtain a greater mechanoluminescent intensity, is 250 parts by weight with respect to 100 parts by weight of the synthetic resin. be. By blending such amounts of the stress-stimulated luminescent material and the inorganic compound and setting the weight ratio of the stress-stimulated luminescent material to the inorganic compound within the preferred range of stress-stimulated luminescent material/inorganic compound = 2/1 to 9/1. , a higher mechanoluminescence intensity can be obtained.

In the mechanoluminescent resin composition of the present invention, the mechanoluminescent material is preferably europium-activated strontium aluminate (hereinafter, europium-activated strontium aluminate is also referred to as SAO).
Europium-activated strontium aluminate is a substance having a high mechanoluminescent intensity, and is therefore suitable as a substance to be used in a mechanoluminescent resin composition.

In the mechanoluminescent resin composition of the present invention, the inorganic compound is preferably at least one selected from the group consisting of magnesium fluoride, calcium fluoride, silicon dioxide, barium sulfate and aluminum oxide.
Since these inorganic compounds do not have a high refractive index and are less expensive than stress-stimulated luminescent materials, these inorganic compounds provide stress-stimulated luminescent resin compositions with higher stress-stimulated luminescent intensity while suppressing cost increases. suitable for

In the mechanoluminescent resin composition of the present invention, the inorganic compound preferably has an average particle size of 0.4 μm to 1.5 μm.
When the average particle size of the inorganic compound is 0.4 μm to 1.5 μm, the stress-stimulated luminescent material receives a sufficiently large force due to the contact between the stress-stimulated luminescent material and the inorganic compound, so that the stress-stimulated luminescent intensity can be sufficiently increased. can.

In the mechanoluminescent resin composition of the present invention, the inorganic compound preferably has a refractive index of 1.35 to 1.80.
When the refractive index of the inorganic compound is within the above range, the mechanoluminescent intensity can be increased.

In the mechanoluminescent resin composition of the present invention, the synthetic resin is at least one selected from urethane resins, epoxy resins, acrylic resins, polyester resins, alkyd resins, silicone resins, fluororesins and modified products thereof. is preferred.
When the synthetic resin is made of these resins, the resin composition has excellent mechanoluminescent intensity and is suitable for application. Judgment can be easily made.

The mechanoluminescent resin composition of the present invention preferably has a pencil hardness of 2H to 4H when the synthetic resin is cured at room temperature.
When the pencil hardness of the cured synthetic resin is high, the mechanoluminescent intensity generally tends to be high, and the effect of blending the inorganic compound into the mechanoluminescent resin composition may not be obtained. On the other hand, when the pencil hardness of the synthetic resin is about 2H to 4H and is not so high, the effect of increasing the stress-induced luminescence intensity by blending the inorganic compound into the stress-induced luminescence resin composition is likely to appear.
In addition, when considering the application of applying the mechanoluminescent resin composition to a large structure, it is difficult to actually use a curing method that heats after application. It is preferable to think

The method for increasing the mechanoluminescent intensity of a mechanoluminescent resin composition of the present invention comprises adding an inorganic compound to a mechanoluminescent resin composition containing a mechanoluminescent material and a synthetic resin to increase the stress of the mechanoluminescent resin composition. A method for increasing luminous intensity, wherein the mechanoluminescent material has an average particle size larger than that of the inorganic compound, and the inorganic compound has a refractive index of 1.35 to 1.90. characterized by the use of

When an inorganic compound having an average particle size and a refractive index defined within a predetermined range is added to a stress-stimulated luminescent resin composition containing a stress-stimulated luminescent material and a synthetic resin, a stress-stimulated luminescent resin composition containing no inorganic compound is obtained. In comparison, the mechanoluminescent intensity of the mechanoluminescent resin composition can be increased.
With this method, the mechanoluminescent intensity of the mechanoluminescent resin composition can be increased without excessively increasing the content of the mechanoluminescent material, which is an expensive material.

In the method for increasing the mechanoluminescent intensity of a mechanoluminescent resin composition of the present invention, the mechanoluminescent resin composition may be prepared by mixing the mechanoluminescent material, the synthetic resin, and the inorganic compound at once.
Adding an inorganic compound to a stress-stimulated luminescent resin composition containing a stress-stimulated luminescent material and a synthetic resin is limited to the process of first mixing the stress-stimulated luminescent material and synthetic resin and then adding the inorganic compound. is not. Since it is sufficient to obtain a mechanoluminescent resin composition as a mixture of a mechanoluminescent material, a synthetic resin, and an inorganic compound, the mechanoluminescent material, a synthetic resin, and an inorganic compound are mixed at once to obtain a mechanoluminescent resin composition. may be prepared.

According to the stress-stimulated luminescent resin composition of the present invention, it is possible to provide a stress-stimulated luminescent resin composition having a higher stress-stimulated luminescent intensity without excessively increasing the content of the stress-stimulated luminescent material.

The mechanoluminescent resin composition of the present invention is described below.
The mechanoluminescent resin composition of the present invention is
A stress-stimulated luminescent resin composition containing a stress-stimulated luminescent material, an inorganic compound, and a synthetic resin,
The average particle size of the mechanoluminescent material is larger than the average particle size of the inorganic compound,
The inorganic compound has a refractive index of 1.35 to 1.90.

<Mechanoluminescent material>
The stress-stimulated luminescent material that can be preferably used in the stress-stimulated luminescent resin composition of the present invention is described below.
This mechanoluminescent material is preferably a mechanoluminescent material based on strontium aluminate, such as a europium-activated strontium aluminate-based mechanoluminescent material.

Strontium aluminate is a compound generally represented by _SrxAlyOz (0< _x , 0< _y , 0<z). Specific examples of strontium aluminate include, but are not limited to, various compounds such as SrAl ₂ O ₄ , SrAl ₄ O ₇ , Sr ₄ Al ₁₄ O ₂₅ , SrAl ₁₂ O ₁₉ , and Sr ₃ Al ₂ O ₆ . ing.

The strontium aluminate is an alumina raw material or aluminum hydroxide containing at least one alumina selected from θ-alumina, κ-alumina, δ-alumina, η-alumina, χ-alumina, γ-alumina, and ρ-alumina, and a strontium source. It is preferably synthesized from Normally, "alumina" often refers to inexpensive and general-purpose α-alumina, but if so-called activated alumina such as θ-alumina or aluminum hydroxide is used as a raw material, a higher luminous intensity is achieved than when α-alumina is used. Because we can.

The activator preferably contains europium (Eu) ions. Although the amount of Eu ions contained in the mechanoluminescent material is not particularly limited, it is 0.0001 to 0.01 mol, preferably 0.0005 to 0.01 mol, more preferably 0.0005 to 0.01 mol, per 1 mol of strontium aluminate. 0005 to 0.005 mol. If the amount of Eu ions is too small, sufficient emission intensity cannot be achieved, and if the amount is too large, the emission intensity will saturate and other physical properties may be affected.

The mechanoluminescent material may further contain a co-activator. Examples of the co-activator include, but are not particularly limited to, compounds or ions of rare earth elements other than Eu. Examples of rare earth elements other than Eu include one or more selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc. elements. These are preferable because substitution with elements having different ionic radii and valences results in the formation of lattice defects, making the crystal structure more easily distorted, resulting in improved mechanoluminescent performance. Among them, Nd, Dy, and Ho are particularly preferred as the co-activator because high emission luminance can be obtained.
Moreover, examples of the compounds of the rare earth elements include carbonates, oxides, chlorides, sulfates, nitrates, and acetates of the elements.

Further, a dispersing agent for enhancing the dispersibility of particles may be added to the raw material composition for stress luminescent material, which is a composition used for producing the stress luminescent material. Examples of dispersants include, but are not limited to, anionic surfactants and nonionic surfactants. Examples of anionic surfactants include ammonium polycarboxylate, sodium polycarboxylate, and sodium hexametaphosphate. Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene Examples include mono fatty acid esters, polyoxyethylene sorbitan mono fatty acid esters, and the like. These may be used alone or in combination of two or more.

In addition, a flux component may be added to the raw material composition for the mechanoluminescent material to improve the crystallinity of the particles. The flux component is not particularly limited, but is magnesium fluoride, aluminum fluoride, ammonium fluoride, sodium chloride, potassium chloride, lithium chloride, ammonium bromide, ammonium iodide, potassium iodide, sodium hydroxide, hydroxide Compounds such as potassium, ammonium sulfate, sodium sulfate, potassium sulfate, sodium nitrate, ammonium nitrate, boric acid, and sodium borate. These may be used alone or in combination of two or more.

Alternatively, the surface of the mechanoluminescent material may be coated with a silane coupling agent and heat-treated to increase the water resistance of the mechanoluminescent material.
The silane coupling agent preferably contains trialkoxysilane.
Further, the substituent other than the alkoxy group of the trialkoxysilane is preferably a hydrocarbon group having 3 or more carbon atoms.
According to the silane coupling agent as described above, hydrophobicity can be enhanced by the structure of the substituent other than the alkoxy group, so that the silane coupling agent can be used as a mechanoluminescent material with further excellent water resistance.

Moreover, the silane coupling agent is preferably a silane coupling agent having a fluoroalkyl group.
When the silane coupling agent has a fluoroalkyl group, the hydrophobicity can be enhanced, and therefore, it can be used as a stress-stimulated luminescent material with further excellent water resistance.

Also, the silane coupling agent is preferably 3,3,3-trifluoropropyltrimethoxysilane.
When 3,3,3-trifluoropropyltrimethoxysilane is used, it can be used as a mechanoluminescent material with particularly excellent water resistance.

Further, a stress-stimulated luminescent material having a surface-treated layer is prepared by mixing a stress-stimulated luminescent material and a phosphoric acid compound to prepare a slurry, and pulverizing the stress-stimulated luminescent material so that the surface of the stress-stimulated luminescent material is modified with the phosphoric acid compound. good too.
A mechanoluminescent material having such a surface treatment layer is also preferable because it becomes a mechanoluminescent material having sufficient water resistance.

The phosphoric acid compound is not particularly specified, and both inorganic phosphates and organic phosphates can be used. Among them, water-soluble salts (including phosphoric acid) are preferred, specifically selected from the group consisting of ammonium phosphate, sodium phosphate, potassium phosphate, sodium polyphosphate, sodium hexametaphosphate, and phosphoric acid. At least one is preferred.

<Method for producing mechanoluminescent material>
The method for producing the mechanoluminescent material is not particularly limited. When the mechanoluminescent material is a europium-activated strontium aluminate-based mechanoluminescent material, it can be obtained by reacting alumina or aluminum hydroxide, a strontium compound, and a europium compound.
Examples of strontium compounds include, but are not limited to, strontium carbonate, strontium oxide, strontium hydroxide, strontium halides (such as strontium chloride), strontium sulfate, strontium nitrate, and strontium hydrogen phosphate.
The europium compound is not particularly limited, and examples thereof include europium carbonate, europium oxide, europium chloride, europium sulfate, europium nitrate, and europium acetate.

The above-described co-activator, dispersant, and flux component may be added to the raw material composition for the mechanoluminescent material, and the mechanoluminescent material is obtained by mixing and firing these components.

The mixing means for the above components is not particularly limited, and known mixing means can be used. Among them, it is preferable to carry out wet mixing in the presence of a dispersing medium (for example, water) in a reaction vessel equipped with a pulverizer for stirring pulverizing media for efficient mixing. Here, the grinding medium agitating type pulverizer is one in which grinding media are put into a pulverizing vessel and agitated by rocking or rotating (rotating or revolving) the pulverizing vessel together with the material to be pulverized, or A pulverizer that directly agitates and pulverizes Examples of the grinding medium agitating pulverizer are not particularly limited, but one selected from the group consisting of planetary mills, bead mills, and vibration mills is preferable. Among them, a planetary mill involving rotation and revolution is particularly preferable. After wet mixing, the dispersion medium is removed and the mixture is dried to obtain a raw material composition for a mechanoluminescent material.

Furthermore, the stress-stimulated luminescent material can be obtained by firing the raw material composition for the stress-stimulated luminescent material. Firing conditions are not particularly limited, and can be carried out according to a general firing method. For example, the obtained raw material composition for a mechanoluminescent material is fired (for example, at 1000° C. or higher in a reducing atmosphere) and, if necessary, pulverized and granulated to obtain a mechanoluminescent material.

Stress-stimulated luminescent materials are physically and chemically relatively stable under various environments, and lattice defects or lattice defects and carriers in luminescent centers are excited by deformation by applying external mechanical force. and emits light when returning to the base.

<Inorganic compound>
The inorganic compound that can be used in the mechanoluminescent resin composition of the present invention is an inorganic compound having a refractive index of 1.35 to 1.90.
When the refractive index is within this range, the light emitted from the stress-stimulated luminescent material is not hindered from exiting the stress-stimulated luminescent resin composition, and the intensity of the light that can be extracted can be increased. Further, it is more preferable that the inorganic compound has a refractive index of 1.35 to 1.80.
The refractive index of an inorganic compound in this specification is defined as the refractive index of light with a wavelength of 589.3 nm.

Preferred examples of inorganic compounds include at least one selected from the group consisting of magnesium fluoride, calcium fluoride, silicon dioxide, barium sulfate and aluminum oxide. Silicon dioxide (silica) is more preferred.
The refractive indices of these inorganic compounds are as follows.
Magnesium fluoride: 1.38
Calcium fluoride: 1.40
Silicon dioxide (silica): 1.46
Barium sulfate: 1.64
Aluminum oxide (alumina): 1.76

<Average particle size of stress-stimulated luminescent material and inorganic compound>
In the stress-stimulated luminescent resin composition of the present invention, the average particle size of the stress-stimulated luminescent material is larger than the average particle size of the inorganic compound. In this specification, the average particle size of the mechanoluminescent material and the average particle size of the inorganic compound can be measured using a laser diffraction/scattering particle size distribution analyzer MT3300EX (manufactured by Microtrack Bell).
Also, the ratio of the average particle size of the stress-stimulated luminescent material to the average particle size of the inorganic compound is preferably stress-stimulated luminescent material/inorganic compound=4.8/1 to 1.3/1.

A preferred lower limit for the average particle size of the mechanoluminescent material is 1.5 μm, and a more preferred lower limit is 1.9 μm. A preferable upper limit of the average particle size of the mechanoluminescent material is 10 μm, and a more preferable upper limit is 7 μm. When the average particle size of the mechanoluminescent material is smaller than 1.5 μm, the mechanoluminescent intensity tends to decrease. In general, as the average particle size of the mechanoluminescent material increases, the mechanoluminescent intensity tends to increase.
A preferable lower limit of the average particle size of the inorganic compound is 0.3 μm, a more preferable lower limit is 0.4 μm, and a further preferable lower limit is 0.7 μm. A preferable upper limit of the average particle size of the inorganic compound is 7.7 μm, a more preferable upper limit is 5.4 μm, and a further preferable upper limit is 1.5 μm.

<Synthetic resin>
As the synthetic resin, various resins such as thermosetting resin, room temperature setting resin, ultraviolet setting resin, and radiation setting resin can be used.
Examples include at least one selected from urethane resins, epoxy resins, acrylic resins, polyester resins, alkyd resins, silicone resins, fluorine resins, polyamide resins, vinyl chloride-vinyl acetate resins, chlorinated propylene resins, and modified products thereof. be done.
Among these resins, it is preferable to include an epoxy resin or a urethane resin. Moreover, the synthetic resin is preferably a two-liquid curable resin composed of a main agent and a curing agent.
When using a two-component curing type epoxy resin or a two-component curing type urethane resin as the synthetic resin, it is preferable to first disperse the stress emitting material and the inorganic compound in the main component to obtain the stress emitting material dispersion main agent. A stress-stimulated luminescent resin composition is prepared by mixing a curing agent with this stress-stimulated luminescent material dispersion base agent, and when this is applied to a structure as an epoxy resin-based coating or a urethane resin-based coating, it is added to the structure. The correspondence relationship between the magnitude of the load applied and the brightness of the emitted light is clear, and it is easy to determine the degree of the load applied to the structure.

The synthetic resin is preferably a room temperature curable resin that can be cured at room temperature. If the resin is curable at room temperature, it can be applied to a large structure that is difficult to heat in a heating furnace or the like, and then cured to form a strong coating film.
In this specification, the room temperature is 25° C., and a resin that is cured by being left at 25° C. for 7 days is regarded as a room temperature curable resin.
Further, the synthetic resin itself may not be curable at room temperature, but may be a resin that becomes curable at room temperature by blending a curing agent or a curing catalyst.
Further, it is preferable that the synthetic resin has a pencil hardness of 2H to 4H when cured at room temperature.

<Combination amount of stress-stimulated luminescent material and inorganic compound with respect to synthetic resin>
The total amount of the mechanoluminescent material and the inorganic compound contained in the mechanoluminescent resin composition is preferably 250 parts by weight or more with respect to 100 parts by weight of the synthetic resin. More preferably, it is 280 parts by weight or more. If the total amount of the mechanoluminescent material and the inorganic compound is not mixed with the synthetic resin in a predetermined amount or more, it is difficult to obtain a high emission intensity.

Also, the total amount of the stress-stimulated luminescent material and the inorganic compound contained in the stress-stimulated luminescent resin composition is preferably 350 parts by weight or less with respect to 100 parts by weight of the synthetic resin. More preferably, it is 320 parts by weight or less. If the total amount of the stress-stimulated luminescent material and the inorganic compound is too large relative to the synthetic resin, the composition becomes crumbly and difficult to apply to the structure.

The weight ratio of the stress-stimulated luminescent material to the inorganic compound is preferably 2/1 to 9/1. If the stress-stimulated luminescent material is not contained in a predetermined ratio or more, it is difficult to obtain high luminescence intensity. On the other hand, if the amount of the inorganic compound is too small, the effect of blending the inorganic compound will not be sufficiently exhibited.

<Other materials>
The stress-stimulated luminescent resin composition of the present invention contains a stress-stimulated luminescent material, an inorganic compound, and a synthetic resin, and if necessary, dispersants, thickeners, surface conditioners or leveling agents, curing agents, Additives such as cross-linking agents, antifoaming agents, antioxidants, light stabilizers including ultraviolet absorbers, flame retardants, curing catalysts, bactericides, and adhesion imparting agents can be contained.

As a dispersant, if it is a polymer dispersant, formalin condensate of naphthalene sulfonate [alkali metal (Na, K, etc.) salt, ammonium salt, etc.], polystyrene sulfonate (same as above), polyacrylic acid Salts (same as above), poly(2-4) carboxylic acid (maleic acid/glycerin/monoallyl ether copolymer, etc.) salts (same as above), carboxymethyl cellulose (Mw 2,000-10,000) and polyvinyl alcohol (Mw 2,000 to 100,000).
Low-molecular-weight dispersants include the following.
(1) AO (C2-4) of polyoxyalkylene-type aliphatic alcohols (C4-30), [alkyl(C1-30)]phenols, aliphatic (C4-30) amines and aliphatic (C4-30) amides 1-30 molar adducts.
Aliphatic alcohols include n-, i-, sec- and t-butanol, octanol, dodecanol, etc.; [alkyl(C1-30)]phenols include phenol, methylphenol and nonylphenol; aliphatic amines include Laurylamine, methylstearylamine, and the like; and fatty amides such as stearic acid amide.
(2) Monoester compounds of polyhydric alcohol type C4-30 fatty acids (lauric acid, stearic acid, etc.) and polyhydric (2-6 or higher) alcohols (eg glycerol, pentaerythritol, sorbitol and sorbitan).
(3) Alkali metal (such as Na and K) salts of carboxylate type C4-30 fatty acids (same as above).
(4) Sulfate-type C4-30 aliphatic alcohols (same as above) and AO (C2-4) 1-30 mol adducts of aliphatic alcohols sulfate alkali metal (Na and K etc.) salts and the like.
(5) Sulfonate-type [alkyl (C1-30)] phenol sulfonic acid alkali metal (Na, K, etc.) salts.
(6) Salts of mono- or diphosphates of fatty alcohols of the phosphate type C4-30 (same as above) and AO(C2-4) 1-30 mole adducts of fatty alcohols [alkali metals (Na and K, etc.) salts, quaternary ammonium salts, etc.].
(7) Fatty amines of primary to tertiary amine salt type C4 to 30 [primary (laurylamine, etc.), secondary (dibutylamine, etc.) and tertiary amines (dimethylstearylamine, etc.)] hydrochloride, triethanolamine and monoesters of C4-30 fatty acids (same as above), salts of inorganic acids (hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, etc.).
(8) Quaternary ammonium salt type C4-30 quaternary ammonium (butyltrimethylammonium, diethyllaurylmethylammonium, dimethyldistearylammonium, etc.) inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salts, and the like.

Examples of inorganic dispersants include alkali metal (same as above) salts of polyphosphoric acid and phosphoric acid-based dispersants (phosphoric acid, monoalkyl phosphate, dialkyl phosphate, etc.).

Examples of thickeners include montmorillonite-based clay minerals, bentonite containing these minerals, inorganic filler-based thickeners such as colloidal alumina, and cellulose-based thickeners such as methylcellulose, carboxymethylcellulose, hexylmethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose. urethane resin thickeners; polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl benzyl ether copolymers and other polyvinyl thickeners; polyether resin thickeners such as polyether dialkyl esters, polyether dialkyl ethers, polyether epoxy modified products; Thickeners, associative thickeners such as urethane-modified polyether thickeners, special polymer nonionic thickeners such as polyether polyol-based urethane resins, surfactant-based thickeners such as nonionics, Examples include protein thickeners such as casein, sodium caseinate and ammonium caseinate, and acrylic thickeners such as sodium alginate.

Leveling agents include PEG-type nonionic surfactants (nonylphenol EO 1-40 mol adduct, stearic acid EO 1-40 mol adduct, etc.), polyhydric alcohol-type nonionic surfactants (sorbitan palmitic acid monoester, sorbitan stearic acid monoester, sorbitan stearic acid triester, etc.), fluorine-containing surfactant (perfluoroalkyl EO 1-50 mol adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine, etc.), and modified silicone oil [polyether-modified silicone oil, (meth)acrylate-modified silicone oil, etc.] and the like.

Curing agents for polyols used to synthesize urethane resins include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and tolylene diisocyanate. , hydrogenated tolylene diisocyanate, and lysine diisocyanate. Also included are nurate and buret forms of the above polyisocyanate compounds, copolymers of polyisocyanate compounds, and adducts of polyisocyanate compounds and polyols such as ethylene glycol, propylene glycol and trimethylolpropane. The above polyol curing agents may be used alone or in combination of two or more.
Curing agents for epoxy resins include acid anhydrides, polyamide resins, amine adducts, polymercaptans, imidazoles, and isocyanates.

Examples of cross-linking agents include melamine resins, urea resins, polyisocyanate compounds, blocked polyisocyanate compounds, epoxy compounds or resins, carboxyl group-containing compounds or resins, acid anhydrides, alkoxysilane group-containing compounds or resins, Hydroxymethyl groups such as hexamethoxymethylated melamine, N,N,N',N'-tetrahydroxymethylsuccinamide, tetramethoxymethylated urea, 2,4,6-tetrahydroxymethylated phenol, and methoxymethyl groups , or a compound having an ethoxymethyl group or the like.

Examples of defoaming agents include silicone-based defoaming agents such as silicone oil, dimethylpolysiloxane, organically modified polysiloxane, and fluorine-modified polysiloxane; mineral oil-based defoaming agents; non-silicone/polymer-based defoaming agents; compounds, antifoaming agents containing at least one selected from polyoxyalkylene compounds, and antifoaming agents comprising aliphatic alcohols having 18 or more carbon atoms.

Antioxidants include hindered phenol compounds, phosphite compounds, phosphonite compounds, thioether compounds, and the like.

Light stabilizers containing ultraviolet absorbers include benzophenone-based compounds, benzotriazole-based compounds, aromatic benzoate-based compounds, oxalic acid anilide-based compounds, cyanoacrylate-based compounds and hindered amine-based compounds.

Examples of flame retardants include brominated flame retardants, phosphorus flame retardants, chlorine flame retardants, triazine flame retardants, salts of phosphoric acid and piperazine, and inorganic flame retardants.

Curing catalysts include organic peroxides such as peroxides (t-butyl peroxybenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, etc.) and azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.). , tin octylate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, dioctyltin oxide, Dibutyltin fatty acid salt, zinc 2-ethylhexanoate, zinc octoate, zinc naphthenate, fatty acid zincs, cobalt naphthenate, calcium octylate, copper naphthenate, lead 2-ethylhexanoate, lead octylate and tetra-n- Organic metal derivatives such as salts of metals such as butyl titanate and organic and inorganic acids, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid sulfonic acid compounds, neutralized amines of sulfonic acid compounds, organic amines such as triethylamine, phosphoric acid, pyrophosphoric acid, phosphoric acid mono- or diesters, and the like. Phosphate monoesters include, for example, monooctyl phosphate, monopropyl phosphate, and monolauryl phosphate. Phosphate diesters include, for example, dioctyl phosphate, dipropyl phosphate, and dilauryl phosphate. Furthermore, phosphoric acid compounds such as mono(2-(meth)acryloyloxyethyl)acid phosphate, diazabicycloundecene-based catalysts, Lewis acids, acid anhydrides and the like are included.

The fungicides include copper fungicides such as oxine copper, organic sulfur fungicides such as zineb and maneb, organic chlorine fungicides such as captan and chlorothalonil, benzimidazole fungicides such as thiophanate-methyl, benomyl, carbendazole, and thiabendazole. Dicarboximide fungicides such as iprodione, vinclozoline, and procymidone; acid amide fungicides such as furametpyr; phenylpyrrole fungicides such as fludioxonil; morpholine fungicides such as dimethomorph; Mepanipyrim, cyprodinil, pyrimethanil and other anilinopyrimidine fungicides, triadimefon, triflumizole and other ergosterol biosynthesis inhibitors, chloropicrin, PCNB and other soil fungicides, other fluazinam, o- phenylphenol (OPP), diphenyl, chlorodiphenyl, cresol, 1,2-bis(bromoacetoxy)ethane, cinnamic aldehyde, phenyl acetate, allyl isocyanate, α-methylacetophenone, thymol, perchlorocyclopentadiene, bromoacetic acid, 2,2-dibromo-3-nitrilepropionamide, ethyl chloroacetate, butyl chloroacetate, methyl chloroacetate, 5-chloro-2-methylisothiazolin-3-one, glutaraldehyde, hinokitiol and the like.

<Method for producing stress-stimulated luminescent resin composition>
The mechanoluminescent resin composition of the present invention can be produced by mixing and dispersing a mechanoluminescent material, an inorganic compound, a synthetic resin, and, if necessary, other materials.
For example, the mechanoluminescent resin composition can be produced by mixing the raw materials and using a mixer such as a conical blender, a V blender, a ribbon blender, a Henschel mixer, a Banbury mixer, or a triple roll.
When using a two-component curing type epoxy resin or a two-component curing type urethane resin as the synthetic resin, the stress-stimulated luminescent material dispersion main agent is obtained by dispersing the stress-stimulated luminescent material and the inorganic compound in the main agent, and this stress-stimulated luminescent material dispersion is obtained. It is preferable to mix a curing agent with the main agent.
Note that the procedure for adding other materials is not particularly limited.

<Application of stress-stimulated luminescent resin composition>
The mechanoluminescent resin composition of the present invention is suitable for use in determining the degree of load applied to a structure by applying it to the structure as a paint.
The material and application of the structure whose degree of load is to be determined are not particularly limited, but suitable materials include ordinary paper, synthetic paper, epoxy resin, polyethylene, polyethylene terephthalate, polyester, polypropylene, Polymer materials such as polyvinyl chloride, natural or synthetic rubber, glass, ceramics, metals, wood, artificial or natural fibers, concrete, or combinations thereof, processed products thereof, and the like. In addition, suitable uses for structures include large structures such as buildings, viaducts, bridges, roads, railroad rails, columns, towers, pipelines and tunnels, floor materials, tiles, wall materials, block materials, pavement materials, Building materials such as wood, steel, and concrete; power transmission components such as gears and cams; exterior parts or built-in parts (engine parts, tires, belts, etc.) used in bicycles, automobiles, trains, ships, airplanes, etc.; , bearing retainers, bearings with optical sensors, fastening parts such as screws, bolts, nuts, washers, and the like.

Moreover, the structure to which the stress-stimulated luminescent resin composition is applied may be a material that has anisotropy in breaking strength and has directions in which the breaking strength is strong and weak against load.
Typical examples of materials having anisotropic breaking strength include wood, artificial fibers, and natural fibers. Some ceramics and metals also have anisotropy. Concrete is originally a material that does not have anisotropy, but since anisotropy is substantially present due to hardening conditions at the time of construction, etc., it is preferable to treat it as a material that has anisotropy.
Information about the direction of the load applied to the structure can be obtained by observing the luminescence pattern of the mechanoluminescent resin composition. The importance of the load applied to the structure can be judged by paying attention to the brightness of the emitted light. Even if the brightness of the emitted light itself is high, if it is determined from the pattern of the emitted light that the direction of the load is the direction in which the breaking strength is strong, there is no need to worry about the load so much. This eliminates the need to take excessive measures for maintenance, and facilitates maintenance of structures.
It is also desirable to observe the pattern of light emission over time. If it is possible to observe the pattern of luminescence over time and confirm that the pattern of luminescence has changed, it is possible to obtain information on whether or not structural destruction has occurred in the structure from the change in the pattern.

When the stress-stimulated luminescent resin composition of the present invention is used for the above applications, the stress-stimulated luminescent resin composition is applied to a structure.
The stress-stimulated luminescent resin composition can be applied by any of the usual methods of applying a paint, and is not particularly limited, but includes spray coating, brush coating, roll coating, gravure coating, and bar coating. , a spin coating method, a dipping method, or the like can be used.
After applying the mechanoluminescent resin composition, the resin is preferably cured, preferably at room temperature. In addition, depending on the type of resin composition, it is desirable to fix the resin composition on the surface of the structure by performing heat curing, ultraviolet curing, or the like.
The coating thickness of the resin composition is desirably 1 to 500 μm.
When the coating thickness is less than 1 μm, the absolute amount of the stress-stimulated luminescent material is small, and the luminance of light emission is insufficient, which may make it difficult to measure the load. In addition, even if the coating thickness exceeds 500 μm, the brightness of light emission does not increase so much, which is not economical.

It is desirable that the stress-stimulated luminescent resin composition is usually applied to the entire surface of the structure, and the degree of load applied to the entire structure is determined. However, when determining the degree of load only at a specific portion of the structure, the stress-stimulated luminescent resin composition may be applied only to that specific portion.

When a load is applied to the structure coated with the mechanoluminescent resin composition and the coating film is distorted, the mechanoluminescent material emits light, and the state of the light emission is observed. Specifically, the luminance of light emitted from the mechanoluminescent material is measured, and the pattern of light emission is observed. Information on the amount of strain and the rate of change in the amount of strain can be obtained from the luminance, and information on the direction in which the load is applied can be obtained from the pattern of light emission.
The luminance of emitted light can be measured by taking a photograph or moving image of a structure emitting light and analyzing the photograph or moving image using image analysis software.
Specifically, image analysis software (for example, ImageJ: manufactured by the National Institutes of Health (NIH)) is used to calculate the brightness of the entire image or a part of the area to be measured, and the background brightness of that part is calculated. The subtracted value can be used as the luminance of mechanoluminescence.

Observation of the light emission pattern is performed visually by an observer so as to recognize a characteristic light emission pattern. In doing so, if the direction in which the load is applied and the strength of the structure are known, the relationship between the pattern of light emission and the direction in which the load is applied and the strength of the structure can be obtained by observing them with reference to them. It is desirable to try to find out the sex.

When measuring the luminance and observing the pattern of light emission periodically after the structure is installed without intentionally applying a load, information on the load applied to the structure at the place where the structure is installed should be collected periodically. can be recorded effectively.
In this case, it is desirable to periodically take pictures (pictures and/or videos) at the place where the structure is installed and keep records.

In addition, when intentionally applying a load to a structure, use a device for strength testing of materials (tensile tester, compression tester, bending tester, etc.) to apply a load to the structure and observe the state of light emission. By doing so, it is possible to measure the relationship between the value of the load applied to the material and the luminescence behavior.
Conditions for applying a load can comply with the JIS regulations regarding materials for structures.

Other uses of the mechanoluminescent resin composition of the present invention include storage batteries, valve seats, water pipes, sprinkler heads, and detection of leaks in non-aqueous electrolyte secondary batteries in which an electrolyte or polymer electrolyte is injected. There is expected. In addition, the stress distribution in the adhesive layer of the adhesive containing the mechanoluminescent material can be visualized, and cracks in the adhesive can be grasped.
Examples of the use of the stress-stimulated luminescent resin composition as an ink composition, bonding agent, or surface coating agent include lamination, which is used in financial institutions, public institutions, credit card companies, the distribution industry, etc. Mailing items such as pressure-bonded postcard sheets containing mechanoluminescent materials in adhesives for use; furniture such as chairs and beds; building materials such as floor materials, tiles, wall materials, blocks, paving materials, wood, steel, concrete, Car navigation devices installed in vehicles; operating devices for operating audio devices, air conditioners, etc.; input devices such as home electric appliances, mobile devices, and electronic computers; Storage means and the like are included.

The method for increasing the mechanoluminescent intensity of a mechanoluminescent resin composition of the present invention comprises adding an inorganic compound to a mechanoluminescent resin composition containing a mechanoluminescent material and a synthetic resin to increase the stress of the mechanoluminescent resin composition. It is a method for increasing the emission intensity. This method is characterized in that the mechanoluminescent material has an average particle size larger than that of the inorganic compound, and the inorganic compound has a refractive index of 1.35 to 1.90. .
When an inorganic compound having an average particle size and a refractive index defined within a predetermined range is added to a stress-stimulated luminescent resin composition containing a stress-stimulated luminescent material and a synthetic resin, a stress-stimulated luminescent resin composition containing no inorganic compound is obtained. In comparison, the mechanoluminescent intensity of the mechanoluminescent resin composition can be increased.
With this method, the mechanoluminescent intensity of the mechanoluminescent resin composition can be increased without excessively increasing the content of the mechanoluminescent material, which is an expensive material.

As the stress-stimulated luminescent material, synthetic resin, and inorganic compound, each material that can be used in the stress-stimulated luminescent resin composition of the present invention can be used, and the preferred blending amount can also be the same.
In addition, other materials that can be contained in the stress-stimulated luminescent resin composition of the present invention and preferred blending amounts can be the same.

In the method for increasing the stress-induced luminescence intensity of a stress-induced luminescence resin composition of the present invention, the stress-induced luminescence resin composition containing a stress-induced luminescence material and a synthetic resin contains an inorganic By adding a compound, a mechanoluminescent resin composition having an increased (enhanced) mechanoluminescent intensity is obtained.
The order of mixing each component is not limited, but specific examples of the method include the following methods (1) to (4). Also, other materials may be mixed at any stage.
(1) A method of mixing a mechanoluminescent material, a synthetic resin and an inorganic compound at once to prepare a mechanoluminescent resin composition having increased (enhanced) mechanoluminescent intensity (2) Mixing a mechanoluminescent material and a synthetic resin (3) Mixing a stress-stimulated luminescent material and an inorganic compound. (4) Mixing a synthetic resin and an inorganic compound to prepare a resin composition. , a method of mixing a mechanoluminescent material to prepare a mechanoluminescent resin composition with increased (enhanced) mechanoluminescent intensity

The following examples are provided to illustrate the invention in detail. However, the present invention is not limited by these examples.

(Example 1)
Strontium carbonate (manufactured by Sakai Chemical Industry, SW-K, 23.466 g), europium oxide (manufactured by Shin-Etsu Chemical, 0.311 g), and aluminum oxide (manufactured by Iwatani Chemical, RA-40, 17.933 g) were weighed, and water was added. (200 mL) and slurried, 3 mm diameter alumina balls (SSA-999W, manufactured by Nikkato, 190 g) were used as grinding media, and a planetary ball mill was used to disperse, grind, and mix the slurry to generate mechanoluminescent slurry. A raw material composition for materials was obtained. The particle size distribution of the slurry was measured using sodium hexametaphosphate as a dispersing agent and using a laser diffraction/scattering particle size distribution analyzer Microtrac MT3300EX. The resulting slurry was evaporated to dryness at 130° C., and the obtained solid matter was pulverized in a mortar to obtain a raw material composition for a mechanoluminescent material in powder form. Next, 20 g of the raw material composition for a mechanoluminescent material was filled in an alumina crucible, heated to 1200° C. at a rate of 200° C./hour in a reducing atmosphere (nitrogen containing 2% hydrogen), maintained as it was for 4 hours, and heated to 1200° C. The temperature was lowered to room temperature at °C/h.
The baked product thus obtained was pulverized in an alcohol solvent using a planetary ball mill, filtered, and dried to obtain a mechanoluminescent material as a powder.
22.5 g of a europium-activated strontium aluminate-based stress-stimulated luminescent material represented by SrAl ₂ O ₄ :Eu ²⁺ (average particle size 1.9 μm) obtained by the above method, spherical particles having an average particle size of 1.5 μm as an inorganic compound Silica (manufactured by Sakai Chemical Industry Co., Ltd., Sciqas (registered trademark), refractive index: 1.46) 4.5 g, two-component curing type epoxy resin main agent 6.0 g (Devcon, Devcon ET main agent) and dilution solvent 8.0 g (Kansai Paint, Selva 1051 Lacquer Thinner) was weighed into a 70 ml mayonnaise jar. Then, 50.0 g of glass beads with a diameter of 1.0 mm (Unibeads, manufactured by Union) were added as a dispersing medium, and dispersed for 20 minutes using a paint shaker (manufactured by RED DEVIL) to prepare a mechanoluminescent material dispersing agent.
After mixing 1.5 g of a curing agent (Devcon ET curing agent manufactured by Devcon) with 20.0 g of the prepared mechanoluminescent material dispersion main agent, an aluminum test piece (material: A1050P, width 35 mm, length 150 mm, 0.8 mm thick) was applied by air spray. The air spray used for coating was an air brush HP-TR1 manufactured by Anest Iwata.
The coating film was prepared so as to have an area of 17 mm×17 mm at the center of the test piece. By curing at room temperature (25° C.) for 7 days, a membranous stress-stimulated luminescent resin composition having a thickness of 117 μm was produced.
In the produced mechanoluminescent resin composition, the blending amount (22.5 g) of the mechanoluminescent material was 250 parts by weight with respect to 100 parts by weight of the synthetic resin (9.0 g of the non-volatile content after curing of the main agent and the curing agent). The amount of the inorganic compound (4.5 g) is 50 parts by weight with respect to 100 parts by weight (9.0 g) of the synthetic resin.
In a dark room for evaluation, the coating film of the test piece was irradiated with ultraviolet rays of 365 nm for 1 minute to excite it, and then the irradiation was stopped and the condition was set to wait for 3 minutes. Then, using a universal material testing machine (TGI-50kN, manufactured by Minebea), the distance between chucks was set to 100mm, and the strain was applied to the test piece at a deformation rate of 20mm/min. (manufactured by Hamamatsu Photonics, H7827-011) was used to evaluate mechanoluminescent properties.
Strain measurement is performed by attaching a strain gauge (KFG-5-120-C1-23L3M3R, manufactured by Kyowa Dengyo Co., Ltd.) on the opposite side of the surface where the coating film is formed and pulling it. Directional strain was measured.
The mechanoluminescence intensity when the strain amount reached 2000 μST was shown as a relative value with the mechanoluminescence intensity of Comparative Example 1, which will be described later, being 100.
The synthetic resin (epoxy resin) used in Example 1 had a pencil hardness of 4H when cured at room temperature.

(Examples 2-5)
A stress-stimulated luminescent resin composition was prepared in the same manner as in Example 1, except that the type of inorganic compound, the average particle size, or the blending amount was changed as shown in Table 1, and the relative stress-stimulated luminescence intensity was evaluated.

(Comparative Examples 1 to 4)
In Comparative Example 1, a mechanoluminescent resin composition was prepared in the same manner as in Example 1 except that no inorganic compound was used, and the relative mechanoluminescent intensity was evaluated.
In Comparative Example 2, a stress-stimulated luminescent resin composition was prepared in the same manner as in Example 1, except that no inorganic compound was used and the blending amount of the stress-stimulated luminescent material was 300 parts by weight per 100 parts by weight of the synthetic resin. was prepared and the relative mechanoluminescence intensity was evaluated.
In Comparative Example 3, a mechanoluminescent resin composition was prepared in the same manner as in Example 1 except that zinc oxide having a refractive index of 2.00 and an average particle size of 0.6 μm was used as the inorganic compound. Relative mechanoluminescence intensity was evaluated.
In Comparative Example 4, a mechanoluminescent resin composition was prepared in the same manner as in Example 1 except that silicon dioxide having a refractive index of 1.46 and an average particle size of 17.8 μm was used as the inorganic compound. , evaluated the relative mechanoluminescence intensity.
Table 1 summarizes the above results of each example and comparative example.

(Example 6)
A mechanoluminescent resin composition was prepared in the same manner as in Example 1 except that the amount of europium-activated strontium aluminate as a mechanoluminescent material was changed to 18.0 g, and the relative mechanoluminescent intensity was evaluated.
In the prepared mechanoluminescent resin composition, the blending amount (18.0 g) of the mechanoluminescent material was 200 parts by weight with respect to 100 parts by weight of the synthetic resin (9.0 g of the non-volatile content after curing of the main agent and the curing agent). The amount of the inorganic compound (4.5 g) is 50 parts by weight with respect to 100 parts by weight (9.0 g) of the synthetic resin.

(Example 7)
A stress-stimulated luminescence resin composition was prepared in the same manner as in Example 6, except that the amount of spherical silica as the inorganic compound was changed to 9.0 g, and the relative stress-stimulated luminescence intensity was evaluated.

(Comparative Example 5)
In Comparative Example 5, a mechanoluminescent resin composition was prepared in the same manner as in Example 6 except that no inorganic compound was used, and the relative mechanoluminescent intensity was evaluated.
Table 2 summarizes the above results of each example and comparative example.

As shown in Table 1, it was found that by blending an inorganic compound, high stress-stimulated luminescent intensity can be exhibited even if the blended amount of the stress-stimulated luminescent material is the same.
In addition, zinc oxide having a refractive index of 2.00 did not improve the mechanoluminescence intensity even when blended.
In Comparative Example 2, the compounding amount of the mechanoluminescent material was 300 parts by weight with respect to 100 parts by weight of the synthetic resin. It is compounded.
Comparing the results of Examples with the results of Comparative Example 2, Examples 1 to 3 and 5 obtained mechanoluminescent intensity greater than that of Comparative Example 2. From this, it was found that a higher mechanoluminescent intensity can be obtained by blending an inorganic compound even if the blending amount of the mechanoluminescent material is reduced. Further, as shown in Table 2, even when the blending amount of the mechanoluminescent material is as small as 200 parts by weight with respect to 100 parts by weight of the synthetic resin, high mechanoluminescent intensity can be exhibited by blending the inorganic compound. I found that it can be done.

Claims (9)

A stress-stimulated luminescent resin composition containing a stress-stimulated luminescent material, an inorganic compound, and a synthetic resin,
The mechanoluminescent material is europium-activated strontium aluminate,
The stress-stimulated luminescent material has an average particle size of 1.5 to 7 μm, which is larger than the average particle size of the inorganic compound,
The inorganic compound has a refractive index of 1.35 to 1.90,
The total amount of the stress-stimulated luminescent material and the inorganic compound contained in the stress-stimulated luminescent resin composition is 250 parts by weight or more with respect to 100 parts by weight of the synthetic resin, and
A stress-stimulated luminescent resin composition, wherein the weight ratio of the stress-stimulated luminescent material to the inorganic compound is 2/1 to 9/1. 2. The mechanoluminescent resin composition according to claim 1, wherein said inorganic compound is at least one selected from the group consisting of magnesium fluoride, calcium fluoride, silicon dioxide, barium sulfate and aluminum oxide. 3. The mechanoluminescent resin composition according to claim 1, wherein the inorganic compound has an average particle size of 0.4 μm to 1.5 μm. The mechanoluminescent resin composition according to any one of claims 1 to 3, wherein the inorganic compound has a refractive index of 1.35 to 1.80. 5. The method according to any one of claims 1 to 4 , wherein the ratio of the average particle size of the stress-stimulated luminescent material to the average particle size of the inorganic compound is stress-stimulated luminescent material/inorganic compound = 4.8/1 to 1.3/1. The mechanoluminescent resin composition. The stress according to any one of claims 1 to 5 , wherein the synthetic resin is at least one selected from urethane resins, epoxy resins, acrylic resins, polyester resins, alkyd resins, silicone resins, fluorine resins and modified products thereof. A luminescent resin composition. The mechanoluminescent resin composition according to any one of claims 1 to 6 , wherein the synthetic resin has a pencil hardness of 2H to 4H when cured at room temperature. A method for increasing the mechanoluminescent intensity of a mechanoluminescent resin composition by adding an inorganic compound to the mechanoluminescent resin composition containing a mechanoluminescent material and a synthetic resin,
The mechanoluminescent material is europium-activated strontium aluminate,
The stress-stimulated luminescent material has an average particle size of 1.5 to 7 μm and is larger than the average particle size of the inorganic compound, and the inorganic compound has a refractive index of 1.35 to 1.90. use,
The total amount of the stress-stimulated luminescent material and the inorganic compound contained in the stress-stimulated luminescent resin composition is 250 parts by weight or more with respect to 100 parts by weight of the synthetic resin, and
A method for increasing the mechanoluminescent intensity of a mechanoluminescent resin composition, wherein the weight ratio of the mechanoluminescent material to the inorganic compound is from 2/1 to 9/1. 9. The method for increasing the mechanoluminescent intensity according to claim 8 , wherein the mechanoluminescent material, the synthetic resin and the inorganic compound are mixed together to prepare a mechanoluminescent resin composition.