TW202233788A - Adhesive particles, adhesive and light-modulating laminate - Google Patents

Abstract

Provided are adhesive particles for which adhesion is increased, aggregations are effectively suppressed, and dripping during heating is suppressed. Adhesive particles according to the present invention each include a thermosetting resin portion and a plurality of inorganic oxide particles, and the inorganic oxide particles are dispersed in the thermosetting resin or the inorganic oxide particles are attached to the surface of the thermosetting resin portion.

Description

Adhesive particles, adhesive, and light-adjusting laminate

The present invention relates to an adhesive particle. Moreover, this invention relates to the adhesive agent and light control laminated body which use the said adhesive particle.

In display devices such as liquid crystal display devices and in-vehicle displays, light control materials such as light control glass and light control films are sometimes used. The light-adjusting material is a material whose light transmittance changes depending on whether an electric field is applied or not, and can adjust the amount of incident light.

In addition, the liquid crystal display element is configured by arranging liquid crystal between two glass or film substrates. For this liquid crystal display element, an adhesive is used in order to bond two glass or film substrates together.

In recent years, as display devices become larger and more flexible, the demand for adhesives with higher adhesion is also increasing. Moreover, in order to further improve the adhesiveness of an adhesive agent, the particle|grains (adhesive particle) which have adhesiveness may be contained in an adhesive agent.

The following Patent Document 1 proposes a thermosetting resin-coated particle comprising: a spherical core particle having a hydrophobic substituent introduced on the surface thereof; and a thermosetting resin layer having the hydrophobic substituent interposed therebetween. coating the surface of the core particles. The said thermosetting resin-coated particle can be used for a liquid crystal display device. The thermosetting resin layer includes: a radically polymerizable acrylate-based prepolymer having a softening point of 40°C to 150°C, and a radical polymerization initiator that generates radicals by heating to a temperature of 60°C to 150°C . Patent Document 1 uses a method (hybridization method) in which core particles and fine particles covering the surface of the core particle are collided in a high-speed airflow, and a resin layer is formed on the surface of the core particle by the heat.

The following Patent Document 2 proposes an adhesive spacer for a liquid crystal display device including seed particles and an adhesive layer derived from adhesive fine particles. The said adhesive layer coats the surface of the said seed particle. The above-mentioned adhesive fine particles are polymer particles containing a structural component derived from a specific polymerizable monomer having a long-chain alkyl group in an amount of 0.1% by weight or more and less than 50% by weight. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-026692 [Patent Document 2] Japanese Patent Laid-Open No. 2003-177409

[Problems to be Solved by Invention]

Regarding the particles formed by the hybridization method as described in Patent Document 1, there is a problem that the adhesive force between the core particles and the resin layer is insufficient, and the resin layer is easily peeled off from the core particles. Moreover, when this particle|grain is heated, the thermosetting resin on the particle|grain surface may melt|dissolve, and dripping may generate|occur|produce, and adhesiveness may fall as a result.

Moreover, as for the conventional adhesive spacer as described in patent document 2, adhesive fine particles may agglomerate each other. As a result, when applying to a substrate or the like by a dispenser or the like, nozzle clogging may occur, or the adhesive spacer may be damaged due to collision with the substrate.

The objective of this invention is to provide the adhesive particle which can improve adhesiveness, can suppress aggregation effectively, and can suppress dripping at the time of heating. Moreover, the objective of this invention is to provide the adhesive agent and light control laminated body which use the said adhesive particle. [Technical means to solve problems]

According to a broader aspect of the present invention, there is provided an adhesive particle comprising a thermosetting resin portion and a plurality of inorganic oxide particles, wherein the inorganic oxide particles are dispersed in the thermosetting resin portion, or the inorganic oxide particles are dispersed in the thermosetting resin portion. The oxide particles adhere to the surface of the thermosetting resin portion.

In one specific aspect of the adhesive particle of this invention, the said inorganic oxide particle is silicon oxide.

In one specific aspect of the adhesive particle of this invention, the thermosetting resin of the said thermosetting resin part is an epoxy resin.

In one specific aspect of the adhesive particle of this invention, the adhesive particle has a base material particle inside, and the said base material particle contains a thermoplastic resin.

In one specific aspect of the adhesive particle of this invention, the said base material particle contains a pigment or a dye.

According to a broader aspect of the present invention, there is provided an adhesive comprising the above-mentioned adhesive particles and a binder.

According to a broader aspect of the present invention, there is provided a light-adjusting laminate including a first substrate, a second substrate, and a light-adjusting layer disposed between the first substrate and the second substrate, wherein the light-adjusting layer The material includes the above-mentioned adhesive particles. [Effect of invention]

The adhesive particle of the present invention includes a thermosetting resin portion and a plurality of inorganic oxide particles, and the inorganic oxide particles are dispersed in the thermosetting resin portion, or the inorganic oxide particles are adhered to the thermosetting resin surface of the department. Since the adhesive particle of this invention has the said structure, adhesiveness can be improved, aggregation can be suppressed effectively, and dripping at the time of heating can be suppressed.

Hereinafter, the details of the present invention will be described.

＜Adhesive particles＞ The adhesive particle of this invention contains a thermosetting resin part, and a some inorganic oxide particle. In the adhesive particle of this invention, the said inorganic oxide particle is dispersed in the said thermosetting resin part, or the said inorganic oxide particle is attached to the surface of the said thermosetting resin part. As for the said adhesive particle, the said inorganic oxide particle may be disperse|distributed in the said thermosetting resin part, and the said inorganic oxide particle may be attached to the surface of the said thermosetting resin part. It is preferable that the said inorganic oxide particle is disperse|distributed in the said thermosetting resin part from a viewpoint of further improving adhesiveness and preventing further damage from collision with a board|substrate at the time of application|coating.

Since the adhesive particle of this invention has the said structure, aggregation can be suppressed effectively. As a result, when apply|coating to a board|substrate etc. by a dispenser etc., dischargeability can be made favorable. Specifically, nozzle clogging is less likely to occur during coating. In addition, particle breakage due to collision with the substrate can be prevented.

Moreover, since the adhesive particle of this invention has the said structure, adhesiveness can be improved. The adhesive particles of the present invention can be bonded by thermosetting the above-mentioned thermosetting resin portion.

Moreover, since the adhesive particle of this invention has the said structure, it can suppress the dripping which generate|occur|produces by melting the thermosetting resin part at the time of heating, and can maintain high adhesiveness. In addition, contamination caused by dripping can be prevented.

The above-mentioned adhesive particles are suitably used for an adhesive. Moreover, the said adhesive particle can be used for a light control material, a light control layer, and a light control laminated body. The said adhesive particle can be used as a spacer for light control glass, and can also be used as a spacer for light control films. The said adhesive particle may be the adhesive particle for light control laminated bodies.

The shape of the said adhesive particle is not specifically limited. A spherical shape may be sufficient as the shape of the said adhesive particle, a shape other than a spherical shape may be sufficient, and a shape, such as a flat shape, may be sufficient as it. In addition, the spherical shape is not limited to a true spherical shape, and includes a substantially spherical shape, for example, a shape with an aspect ratio (major diameter/minor diameter) of 1.5 or less.

FIG. 1 is a cross-sectional view showing an adhesive particle according to a first embodiment of the present invention.

The adhesive particle 1 shown in FIG. 1 includes a particle body 2 (thermosetting resin portion) and a plurality of inorganic oxide particles 3 . In the adhesive particle 1, the inorganic oxide particles 3 are dispersed in the particle body 2 (thermosetting resin part). The particle body 2 (thermosetting resin portion) is formed of a thermosetting resin, and contains a thermosetting resin.

FIG. 2 is a cross-sectional view showing an adhesive particle according to a second embodiment of the present invention.

The adhesive particle 11 shown in FIG. 2 includes the base material particle 14 , the coating part 12 , and a plurality of inorganic oxide particles 13 . In the adhesive particles 11 , the inorganic oxide particles 13 are dispersed in the coating portion 12 . The adhesive particle 11 has the base material particle 14 inside. In the adhesive particle 11 , the coating part 12 is in contact with the surface of the base material particle 14 and coats the surface of the base material particle 14 . The adhesive particles 11 are coated particles in which the surfaces of the substrate particles 14 are coated with the coating portion 12 . In the adhesive particle 11, the coating part 12 is a single-layer coating layer. In the adhesive particle 11, the coating part 12 is a thermosetting resin part. The thermosetting resin portion is formed of a thermosetting resin, and includes a thermosetting resin.

The main difference between the adhesive particle 1 shown in FIG. 1 and the adhesive particle 11 shown in FIG. 2 is the base material particle 14 . That is, the base material particle 14 is formed in the adhesive particle 11 on the other hand, while the base material particle is not formed in the adhesive particle 1 .

3 is a cross-sectional view showing an adhesive particle according to a third embodiment of the present invention.

The adhesive particle 21 shown in FIG. 3 includes the base material particle 24 , the coating part 22 , and a plurality of inorganic oxide particles 23 . Among the adhesive particles 21 , the inorganic oxide particles 23 adhere to the surface of the coating portion 22 . The adhesive particles 21 have base particles 24 . In the adhesive particle 21 , the coating portion 22 is in contact with the surface of the base material particle 24 and coats the surface of the base material particle 24 . The adhesive particles 21 are coated particles in which the surfaces of the substrate particles 24 are coated with the coating portion 22 . In the adhesive particle 21, the coating part 22 is formed of a plurality of particles. In the adhesive particle 21, the coating part 22 contains a thermosetting resin part. In the adhesive particle 21, the particle which forms the coating part 22 contains a thermosetting resin.

The main difference between the adhesive particles 11 and the adhesive particles 21 is the covering portion 12 and the covering portion 22 . That is, the coating part in the adhesive particle 11 is a single-layer coating layer, whereas the coating part in the adhesive particle 21 is formed by a plurality of particles. In the adhesive particle 1 and the adhesive particle 11, the said inorganic oxide particle is dispersed in the said thermosetting resin, and in the adhesive particle 21, the said inorganic oxide particle adheres to the surface of the said thermosetting resin part.

Since the adhesive particle 11 and the adhesive particle 21 have the base material particle 14 and the base material particle 24, they are excellent in gap controllability. Therefore, the adhesive particles 11 and the adhesive particles 21 are suitably used as spacers for light-adjusting laminates and the like. The adhesive particle 11 and the adhesive particle 21 are suitably used as a spacer for light control glass and a spacer for light control films. For example, in the light-adjusting laminate in which the above-mentioned adhesive particles are arranged between the substrates, the gap between the substrates can be controlled with high precision, and the uniformity of the thickness between the substrates can be improved. In addition, by suppressing peeling of the conductive film, the light control performance of the light control laminate can be maintained.

In 100% of the total surface area of the base material particles, the surface area (covering ratio) covered by the coating portion is preferably 20% or more, more preferably 50% or more, still more preferably 80% or more, particularly preferably 85% or more . The upper limit of the above-mentioned coverage is not particularly limited. The said coverage rate may be 100% or less, and may be 99% or less. Adhesion can be further improved as the said coverage ratio is more than the said lower limit. Moreover, when the said adhesive particle is used as a gap material, a gap can be controlled more precisely.

In 100% of the total surface area of the base material particles, the surface area (covering ratio) covered by the coating portion is obtained by observing the adhesive particles with an electron microscope or an optical microscope, and calculating the coverage by the coating portion. The percentage of the surface area relative to the projected area of the substrate particles.

From the viewpoint of further improving the adhesion, the thickness of the coating portion is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1 μm or more, preferably 10 μm or less, and more preferably 7 μm or less. , more preferably 5 μm or less. In addition, when the said covering part is formed by a plurality of layers, the thickness of the said covering part means the thickness of the whole said covering part.

The thickness of the said coating part can be calculated from the difference between the particle diameter of the said base material particle and the particle diameter of the said particle.

From the viewpoint of further improving the adhesiveness, the CV value of the particle diameter of the adhesive particles is preferably 10% or less, more preferably 7% or less. The upper limit of the CV value of the particle diameter of the adhesive particles is not particularly limited. The CV value of the particle diameter of the said adhesive particle may be 30% or less.

The CV value (coefficient of variation) of the particle diameter of the above-mentioned adhesive particles can be measured as follows.

CV value (%)=(ρ/Dn)×100 ρ: Standard deviation of the particle size of the above-mentioned adhesive particles Dn: the average value of the particle diameters of the above-mentioned adhesive particles

The compressive modulus of elasticity (10% K value) of the above-mentioned adhesive particles at 25°C when compressed by 10% is preferably 10 N/mm ² or more, more preferably 1000 N/mm ² or more, preferably 10000 N/ mm ² or less, more preferably 7000 N/mm ² or less. When the 10% K value is above the above lower limit and below the above upper limit, the gap can be controlled with high accuracy.

The compressive modulus of elasticity (30% K value) of the above-mentioned adhesive particles at 25°C when compressed by 30% is preferably 50 N/mm ² or more, more preferably 2000 N/mm ² or more, preferably 20000 N/ mm ² or less, more preferably 10000 N/mm ² or less. When the 30% K value is above the above lower limit and below the above upper limit, the gap can be controlled with high accuracy.

The said compression elastic modulus (10% K value and 30% K value) of the said adhesive particle can be measured as follows.

Using a micro-compression tester, compress one adhesive particle with a smooth indenter end face of a cylinder (diameter 100 μm, made of diamond) at 25°C, a compression speed of 0.3 mN/sec, and a maximum test load of 20 mN . Measure the load value (N) and the compression displacement (mm) at this time. The above-mentioned compressive elastic modulus (10% K value and 30% K value) can be determined from the obtained measured values by the following formula. As the above-mentioned micro-compression tester, for example, "Fischerscope H-100" manufactured by Fischer Corporation can be used. The above-mentioned compressive elastic modulus (10% K value and 30% K value) of the above-mentioned adhesive particles is preferably determined by the above-mentioned compressive elastic modulus (10% K value and 30% K value) for 50 randomly selected adhesive particles. value) is calculated by arithmetic mean.

10% K value and 30% K value (N/mm ² )=(3/2 ^1/2 )・F・S ^-3/2・R ^-1/2 F: 10% or 30% of adhesive particles occurred Load value during compression deformation (N) S: Compression displacement when the adhesive particle undergoes 10% or 30% compression deformation (mm) R: Radius of the adhesive particle (mm)

The aforementioned compressive elastic modulus generally and quantitatively represents the hardness of the adhesive particles. By using the above-mentioned compressive elastic modulus, the hardness of the adhesive particles can be quantitatively and singly expressed.

From the viewpoint of further improving the adhesiveness, in the following adhesiveness test A, the tensile yield stress of the adhesive particles is preferably 0.03 MPa or more, more preferably 0.05 MPa or more, and still more preferably 0.10 MPa or more. The upper limit of the tensile yield stress of the adhesive particles is not particularly limited. In the following adhesion test A, the tensile stress of the adhesive particles may be 0.03 MPa or less, and may be less than 0.03 MPa.

In addition, from the viewpoint of further improving the adhesiveness, in the following adhesiveness test B, the tensile yield stress of the adhesive particles is preferably 0.05 MPa or more, more preferably 0.07 MPa or more, and still more preferably 0.12 MPa above. The upper limit of the tensile yield stress of the adhesive particles is not particularly limited. In the following adhesiveness test B, the tensile stress of the adhesive particles may be 0.05 MPa or less, and may be less than 0.05 MPa.

(Adhesion Test A) Glass substrates were prepared as the first substrate and the second substrate. On the surface of the 1st board|substrate, adhesive particle was spread|dispersed so that it might become 10 pieces/mm< ² >. Next, according to the method of JIS K6850, it heated at 100 degreeC for 60 minutes with the pressure of 5 kgf/cm< ² >, and adhered the adhesive particle on the 1st, 2nd board|substrate, and produced the test body (test sample). Using a Tensilon universal testing machine, with a tensile speed of 20 mm/min and a load cell rating of 1000 N, the adhesion strength of the obtained test body at 23° C. was measured. This measured value was used as the tensile yield stress of the adhesive particles.

(Adhesion Test B) Glass substrates were prepared as the first substrate and the second substrate. On the surface of the 1st board|substrate, adhesive particle was spread|dispersed so that it might become 10 pieces/mm< ² >. Then, according to the method of JIS K 6850, it heated at 130 degreeC for 60 minutes with the pressure of 5 kgf/cm< ² >, and adhered the adhesive particle on the 1st, 2nd board|substrate, and produced the test body (test sample). Using a Tensilon universal testing machine, with a tensile speed of 20 mm/min and a load cell rating of 1000 N, the adhesion strength of the obtained test body at 23° C. was measured. This measured value was used as the tensile yield stress of the adhesive particles.

As said glass substrate, "S-7213" by Matsunami Glass Industrial Co., Ltd., etc. can be used. As the above-mentioned Tensilon universal material testing machine, "RTI-1310" manufactured by A&D Corporation can be used.

Hereinafter, other details of the adhesive particles will be described. Furthermore, in this specification, "(meth)acrylate" means one or both of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic acid" and "methacrylate". methacrylic acid" or both.

(Thermosetting resin part/Thermosetting resin) In the adhesive particle of the present invention, the particle body of the adhesive particle may include a thermosetting resin portion, the particle body of the adhesive particle may be a thermosetting resin portion, and the coating portion in contact with the surface of the substrate particle may be Including a thermosetting resin portion, the covering portion may be a thermosetting resin portion. In the adhesive particle of this invention, it is preferable that the particle|grain main body of an adhesive particle is a thermosetting resin part. Moreover, in the adhesive particle of this invention, it is preferable that the coating part in contact with the surface of the base material particle is a thermosetting resin part. The said thermosetting resin part may comprise the particle|grain main body of the said adhesive particle, and may comprise the covering part which contacts the surface of a base material particle. The said thermosetting resin part is formed of a thermosetting resin, and contains a thermosetting resin. In addition, the said thermosetting resin part may contain components other than thermosetting resin in the range which does not impair thermosetting property. Components other than the above-mentioned thermosetting resin may be resins.

The above-mentioned covering portion may be formed of one layer. The above-mentioned covering portion may be formed of a plurality of layers. That is, the said coating part may have the laminated structure of 2 or more layers. When the said covering part is formed by a plurality of layers, it is preferable that the outermost layer contains a thermosetting resin part. The above-mentioned coating portion may be formed of a plurality of particles. From the viewpoint of suppressing peeling of the coating portion from the surface of the substrate particle, the coating portion is preferably a single-layer coating layer.

As said thermosetting resin, an epoxy resin, a vinyl ester resin, an unsaturated polyester resin, etc. are mentioned. As for the said thermosetting resin, only 1 type may be used and 2 or more types may be used together.

As said epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, biphenyl type epoxy resin, Phenol novolac type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, phenylene type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentane Ethylene-type epoxy resin, anthracene-type epoxy resin, epoxy resin with adamantane skeleton, epoxy resin with tricyclodecane skeleton, and epoxy resin with tri-nucleus in the skeleton, etc.

As said vinyl ester resin, a bis-type vinyl ester resin, a novolak-type vinyl ester resin, etc. are mentioned.

As said unsaturated polyester resin, the resin etc. obtained by the polycondensation of (alpha), (beta)- unsaturated dicarboxylic acid or its acid anhydride, and diol are mentioned.

It is preferable that the said thermosetting resin contains an epoxy resin from a viewpoint of further improving adhesiveness. From the viewpoint of further improving adhesiveness, the above-mentioned thermosetting resin is preferably an epoxy resin.

When an epoxy resin is used as the material of the said adhesive particle, it is preferable that the said epoxy resin is a polyfunctional epoxy resin. As said polyfunctional epoxy resin, bifunctional epoxy resins, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc., tris-type epoxy resin, and glycidylamine type epoxy resin are mentioned, for example Trifunctional epoxy resins such as tetraphenolethane type epoxy resins, and tetrafunctional epoxy resins such as glycidylamine type epoxy resins, etc. As for the said epoxy resin, only 1 type may be used and 2 or more types may be used together.

Moreover, when using an epoxy resin as the material of the said adhesive particle, it is preferable to use a hardener together with an epoxy resin. The said hardening|curing agent heat-hardens the said epoxy resin. The above-mentioned curing agent is not particularly limited. As said hardener, an imidazole hardener, an amine hardener, a phenol hardener, a thiol hardener, such as a polythiol hardener, an acid anhydride hardener, etc. are mentioned. Only one type of the above-mentioned curing agent may be used, or two or more types may be used in combination. The above-mentioned hardener is preferably an amine hardener from the viewpoint of easily controlling the compressive properties of the above-mentioned adhesive particles within a preferable range.

The above-mentioned imidazole curing agent is not particularly limited. As said imidazole hardener, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole Onium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-symmetric tris-tris, and 2,4-diamino-6-[ 2'-Methylimidazolyl-(1')]-ethyl-symmetric tricyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4 -Methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2-p-toluyl-4-methyl-5-hydroxymethylimidazole, 2- m-tolyl-4-methyl-5-hydroxymethylimidazole, 2-m-tolyl-4,5-dihydroxymethylimidazole, 2-p-tolyl-4,5-dihydroxy In methylimidazole and the like, the 5-position hydrogen atom of 1H-imidazole is substituted with a hydroxymethyl group and the 2-position hydrogen atom is substituted with a phenyl or tolyl imidazole compound, and the like.

The said thiol hardener is not specifically limited. As said thiol hardener, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate, etc. are mentioned.

The above-mentioned amine hardener is not particularly limited. As said amine hardener, ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, 2,5(2,6)-bis(aminomethyl) ) Bicyclo[2.2.1]heptane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro[5.5]undecane, bis(4-aminocyclohexyl) ) methane, phenylenediamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, m-phenylenediamine, diaminodiphenylmethane, diaminophenyl ether, m Xylylenediamine, diaminonaphthalene, diaminomethylcyclohexane, and diaminodiphenyl benzene, etc. The above-mentioned amine hardener is preferably ethylenediamine, hexamethylenediamine, octamethylenediamine, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane , m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylmethane, phenylenediamine, or 2,2-bis[4-(4-aminophenoxy)phenyl]propane. By using these preferable amine hardeners, the compressive properties of the above-mentioned adhesive particles can be easily controlled within a preferable range. From the viewpoint of easily controlling the compressive properties of the adhesive particles within a preferable range, the amine hardener is more preferably ethylenediamine, 2,5(2,6)-bis(aminomethyl)bicyclo[ 2.2.1] Heptane, diaminodiphenylmethane, phenylenediamine, or 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

The said acid anhydride hardening|curing agent is not specifically limited, If it is an acid anhydride which can be used as a hardening|curing agent of thermosetting compounds, such as an epoxy compound, it can be widely used. As said acid anhydride hardener, phthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Formic anhydride, methyltetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, anhydrous of phthalic acid derivatives, maleic anhydride, terresin anhydride, methyl terrestrial Acid anhydride, glutaric anhydride, succinic anhydride, glycerol bis-trimellitic anhydride monoacetate, bi-functional acid anhydride hardeners such as ethylene glycol bis-trimellitic anhydride, tri-functional acid anhydride hardeners such as trimellitic anhydride, and isobenzene Tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, polyazelaic anhydride and other tetrafunctional acid anhydride hardeners and the like.

The content of the thermosetting resin in 100% by weight of the thermosetting resin portion is preferably 50% by weight or more, more preferably 70% by weight or more, more preferably 90% by weight or more, preferably 99.9% by weight Below, it is more preferable that it is 99.7 weight% or less, and it is still more preferable that it is 99.6 weight% or less. When the content of the thermosetting resin is more than or equal to the above lower limit and less than or equal to the above upper limit, adhesiveness can be further improved, and dripping at the time of heating can be further effectively suppressed.

The content of the thermosetting resin is preferably 70 wt % or more, more preferably 90 wt % or more, and most preferably 100 wt % in the total 100 wt % of all resin components contained in the thermosetting resin portion (total). When the content of the thermosetting resin is at least the above lower limit, the adhesiveness can be further improved, and dripping during heating can be further effectively suppressed.

In 100% by weight of the above-mentioned adhesive particles, the content of the above-mentioned thermosetting resin is preferably 2% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, particularly preferably 25% by weight or more, Preferably it is 99.5 weight% or less, More preferably, it is 99 weight% or less, More preferably, it is 98 weight% or less. Adhesiveness can be improved further as content of the said thermosetting resin is more than the said minimum and below the said upper limit, and dripping at the time of heating can be suppressed more effectively.

In the above-mentioned adhesive particles without substrate particles, the content of the thermosetting resin in 100% by weight of the above-mentioned adhesive particles is preferably 70% by weight or more, more preferably 75% by weight or more, and still more preferably 80% by weight. % by weight or more, preferably 99.5% by weight or less, more preferably 99% by weight or less, and still more preferably 98% by weight or less. Adhesiveness can be improved further as content of the said thermosetting resin is more than the said minimum and below the said upper limit, and dripping at the time of heating can be suppressed more effectively.

In the above-mentioned adhesive particles having substrate particles, the content of the thermosetting resin in 100% by weight of the above-mentioned adhesive particles is preferably 2% by weight or more, more preferably 5% by weight or more, and still more preferably 10% by weight % or more, preferably 25% by weight or more, preferably 70% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less. Adhesiveness can be improved further as content of the said thermosetting resin is more than the said minimum and below the said upper limit, and dripping at the time of heating can be suppressed more effectively.

(inorganic oxide particles) As the inorganic oxide particles, silicon oxide, titanium dioxide (titanium oxide), zinc oxide, aluminum oxide, glass, talc, kaolin, bentonite, and zirconium may, for example, be mentioned.

From the viewpoint of further effectively suppressing aggregation and further effectively suppressing dripping during heating, the inorganic oxide particles preferably contain silicon oxide or titanium dioxide, and more preferably contain silicon oxide. From the viewpoint of further improving the adhesiveness and increasing the strength of the adhesive particles, the inorganic oxide particles are preferably silicon oxide or titanium dioxide, and more preferably silicon oxide.

As said silicon oxide, a natural silicon oxide and a synthetic silicon oxide are mentioned. Examples of the synthetic silica include hydrophilic silica and hydrophobic silica. From the viewpoint of stable quality, the above-mentioned silicon oxide is preferably a synthetic silicon oxide, and more preferably a synthetic silicon oxide produced by a vapor phase method.

In 100% by weight of the above-mentioned adhesive particles, the content of the above-mentioned inorganic oxide particles is preferably 0.25% by weight or more, more preferably 0.5% by weight or more, still more preferably 1% by weight or more, particularly preferably 1.9% by weight or more, Preferably it is 20 weight% or less, More preferably, it is 15 weight% or less, More preferably, it is 10 weight% or less. When the content of the inorganic oxide particles is at least the above lower limit and below the above upper limit, the adhesiveness can be further improved, and aggregation can be further effectively suppressed.

The content of the inorganic oxide particles is preferably 0.3 part by weight or more, more preferably 0.6 part by weight or more, more preferably 1 part by weight or more, and particularly preferably 2.5 part by weight or more with respect to 100 parts by weight of the above-mentioned thermosetting resin , the best is 2.9 parts by weight or more. The content of the inorganic oxide particles is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, more preferably 10 parts by weight or less, and particularly preferably 7.6 parts by weight or less with respect to 100 parts by weight of the above-mentioned thermosetting resin . When the content of the inorganic oxide particles is at least the above lower limit and below the above upper limit, the adhesiveness can be further improved, and aggregation can be further effectively suppressed.

In the above-mentioned adhesive particles having no substrate particles, the content of the inorganic oxide particles in 100% by weight of the adhesive particles is preferably 0.4% by weight or more, more preferably 0.9% by weight or more, and still more preferably 1.9% by weight % or more, preferably 19.5 wt % or less, more preferably 14.5 wt % or less, and still more preferably 9.5 wt % or less. When the content of the inorganic oxide particles is at least the above lower limit and below the above upper limit, the adhesiveness can be further improved, and aggregation can be further effectively suppressed.

The content of the inorganic oxide particles is preferably 0.5 part by weight or more, more preferably 1 part by weight or more, more preferably 100 parts by weight of the above-mentioned thermosetting resin, in the above-mentioned adhesive particles having no substrate particles. It is 2 parts by weight or more, particularly preferably 2.5 parts by weight or more. The content of the inorganic oxide particles is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, more preferably 100 parts by weight of the above-mentioned thermosetting resin, in the above-mentioned adhesive particles having no substrate particles. 10 parts by weight or less. When the content of the inorganic oxide particles is at least the above lower limit and below the above upper limit, the adhesiveness can be further improved, and aggregation can be further effectively suppressed.

In the above-mentioned adhesive particles having substrate particles, the content of the inorganic oxide particles in 100% by weight of the adhesive particles is preferably 0.25% by weight or more, more preferably 0.5% by weight or more, and still more preferably 1.0% by weight More than 1.9 weight% or more is especially preferable. In the above-mentioned adhesive particles having substrate particles, the content of the inorganic oxide particles in 100% by weight of the adhesive particles is preferably 12% by weight or less, more preferably 10% by weight or less, and still more preferably 6% by weight the following. When the content of the inorganic oxide particles is at least the above lower limit and below the above upper limit, the adhesiveness can be further improved, and aggregation can be further effectively suppressed.

In the above-mentioned adhesive particles having substrate particles, the content of the above-mentioned inorganic oxide particles is preferably 0.3 parts by weight or more, more preferably 0.6 parts by weight or more, and still more preferably 100 parts by weight of the above-mentioned thermosetting resin. 1.0 parts by weight or more, particularly preferably 2.5 parts by weight or more. The content of the inorganic oxide particles in the adhesive particles having the substrate particles is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, and still more preferably 7.0 parts by weight or less. When the content of the inorganic oxide particles is at least the above lower limit and below the above upper limit, the adhesiveness can be further improved, and aggregation can be further effectively suppressed.

(substrate particles) The said adhesive particle may have a base material particle in the inside of the said adhesive particle, and may not have it. In addition, the adhesive particle having the substrate particle inside the adhesive particle means, for example, like the adhesive particle 11 or the adhesive particle 21, a part of the surface of the substrate particle is covered with a coating layer or a plurality of particles. the coated particles. The adhesive particle which does not have a base material particle in the said adhesive particle means the adhesive particle which does not have a coating part like the adhesive particle 1, for example.

From the viewpoints of suppressing peeling of the coating layer or the coating particles from the surface of the base material particles, further improving the adhesiveness, and controlling the gap with high precision, the base material particles preferably contain a thermoplastic resin.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, and polyisobutylene, and acrylic resins such as polymethyl methacrylate and polymethyl acrylate. , polyvinyl acetal resin, polyester resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, polyurethane resin and polyvinyl alcohol resin, etc. Only one kind of the above-mentioned thermoplastic resins may be used, or two or more kinds thereof may be used in combination.

From the viewpoint of improving the blackness and suppressing the occurrence of light leakage, the base material particles preferably contain a pigment or a dye. Only one type of the above-mentioned pigments or dyes may be used, or two or more types may be used in combination. Furthermore, the so-called light leakage refers to the phenomenon in which the light from the backlight passes through the molten resin portion when the liquid crystal display element is turned on. Leakage of light may result in a decrease in the contrast ratio of the liquid crystal display element, or a decrease in the display quality known as the white point.

As said pigment, carbon black, titanium black, aniline black, iron oxide, lamp black, graphite, copper-chromium composite oxide, copper-chromium-zinc composite oxide, etc. are mentioned. From the viewpoint of improving the blackness and suppressing the occurrence of light leakage, the above-mentioned pigment preferably contains carbon black.

Examples of the above dyes include pyrazole azo dyes, anilino azo dyes, triphenylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxolanes Ethylene dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole methimide dyes, xanthene dyes, phthalocyanine dyes Dyes, benzopyran-based dyes, indigo-based dyes, pyrrolemethine-based dyes, triarylmethane-based dyes, methimine-based dyes, perylene-based dyes, pyrenone-based dyes, quaterrylene-based dyes, and Quinophthalone-based dyes, etc. The above dyes can also be prepared by adding two or more of acid dyes, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azo dyes, disperse dyes, oil-soluble dyes, food dyes and derivatives thereof. Dye, etc., which are mixed to make black.

From the viewpoint of improving the strength of the base material particles and suppressing the occurrence of light leakage, the total content of the pigments and dyes in 100% by weight of the base material particles is preferably 1% by weight or more, more preferably 3% by weight or more, More preferably, it is 5% by weight or more, more preferably 20% by weight or less, more preferably 15% by weight or less, and still more preferably 10% by weight or less.

From the viewpoint of further improving the adhesiveness, the CV value of the particle diameter of the substrate particles is preferably 10% or less, more preferably 7% or less. The upper limit of the CV value of the particle diameter of the substrate particles is not particularly limited. The CV value of the particle size of the above-mentioned substrate particles may be 30% or less.

The CV value (coefficient of variation) of the particle diameter of the above-mentioned substrate particles can be measured as follows.

CV value (%)=(ρ/Dn)×100 ρ: Standard deviation of the particle size of the above-mentioned substrate particles Dn: the average value of the particle diameters of the above-mentioned substrate particles

The 10% K value of the substrate particles is preferably 10,000 N/mm from the viewpoint of preventing damage to the substrate due to collision with the substrate when applying it to the substrate using a dispenser, etc., and further improving the adhesiveness ² or less, more preferably 7000 N/mm ² or less. The lower limit of the 10% K value of the substrate particles is not particularly limited. The 10% K value of the above-mentioned substrate particles may be more than 10 N/mm ² .

The 10% K value of the above-mentioned substrate particles can be measured as follows.

Using a micro-compression tester, a smooth indenter end face of a cylinder (diameter 50 μm, made of diamond) was loaded at 25°C with a maximum test load of 20 mN for 60 seconds, and the substrate particles were compressed under the above conditions. Measure the load value (N) and the compression displacement (mm) at this time. The above-mentioned 10% K value can be calculated|required from the obtained measurement value according to the following formula. As the above-mentioned micro-compression tester, for example, "Fischerscope H-100" manufactured by Fischer Corporation can be used.

10% K value (N/mm ² )=(3/2 ^1/2 )・F・S ^-3/2・R ^-1/2 ) S: Compression displacement when the substrate particles undergo 10% compression deformation (mm) R: Radius of the substrate particles (mm)

From the viewpoint of practicality, the particle diameter of the above-mentioned substrate particles is preferably 0.9 μm or more, more preferably 7.9 μm or more, further preferably 9.9 μm or more, preferably 49 μm or less, and more preferably 29 μm or less. , more preferably 24.5 μm or less.

When the above-mentioned base material particles are true spherical, the particle diameter of the above-mentioned base material particles means diameter, and when the above-mentioned base material particles are in a shape other than true spherical shape, the above-mentioned particle diameter of the base material particles means the assumption. The diameter of a true sphere equivalent to its volume.

In addition, the particle diameter of the said base material particle means the average particle diameter obtained by measuring the said base material particle with the particle diameter measuring apparatus. As a particle diameter measuring apparatus, the particle size distribution measuring machine etc. which use the principles of laser light scattering, resistance value change, image analysis after imaging, etc. are mentioned, for example. Specifically, as a method for measuring the particle diameter of the above-mentioned substrate particles, for example, a method of measuring about 100,000 particle diameters using a particle size distribution analyzer (“Multisizer 4” manufactured by Beckman Coulter) can be exemplified. , to measure the average particle size. The above-mentioned average particle diameter represents the number average particle diameter.

In the adhesive particles having the substrate particles, the content of the substrate particles in 100% by weight of the adhesive particles is preferably 13% by weight or more, more preferably 37% by weight or more, and still more preferably 63% by weight or more, Preferably it is 99 weight% or less, More preferably, it is 94 weight% or less, More preferably, it is 87 weight% or less. Adhesion can be further improved as content of the said base material particle is more than the said minimum and below the said upper limit, and aggregation can be suppressed more effectively.

In the adhesive particles having substrate particles, the content of the substrate particles in 100% by volume of the adhesive particles is preferably 5% by volume or more, more preferably 10% by volume or more, and still more preferably 15% by volume or more, Preferably it is 95 volume % or less, More preferably, it is 85 volume % or less, More preferably, it is 75 volume % or less. Adhesion can be further improved as content of the said base material particle is more than the said minimum and below the said upper limit, and aggregation can be suppressed more effectively.

＜Adhesive＞ The adhesive agent of this invention contains the said adhesive particle and a binder. The above-mentioned adhesive particles are preferably dispersed in a binder and used as an adhesive. The above-mentioned adhesive is suitably used for the light-adjusting layer and the light-adjusting laminate. Only one type of the above-mentioned binder may be used, or two or more types may be used.

The above-mentioned binder is not particularly limited. As the above-mentioned binder, insulating resins are generally used. As a binder resin, a vinyl resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer, an elastomer, etc. are mentioned, for example. Only one type of the above-mentioned binder resin may be used, or two or more types may be used in combination.

As said vinyl resin, a vinyl acetate resin, an acrylic resin, a styrene resin, etc. are mentioned, for example. As said thermoplastic resin, a polyolefin resin, an ethylene-vinyl acetate copolymer, a polyamide resin, etc. are mentioned, for example. As said curable resin, an epoxy resin, a urethane resin, a polyimide resin, an unsaturated polyester resin, etc. are mentioned, for example. Furthermore, the above-mentioned curable resin may be a room temperature curable resin, a thermosetting resin, a light curable resin, or a moisture curable resin. The above curable resin may be used in combination with a curing agent. As said thermoplastic block copolymer, for example, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-benzene Hydrogenated products of ethylene block copolymers, hydrogenated products of styrene-isoprene-styrene block copolymers, etc. As said elastomer, a styrene-butadiene copolymer rubber, an acrylonitrile-styrene block copolymer rubber, etc. are mentioned, for example.

It is preferable that the said adhesive agent and the said adhesive agent contain a thermoplastic component or a thermosetting component. The said adhesive agent and the said adhesive agent may contain a thermoplastic component, and may contain a thermosetting component.

In addition to the above-mentioned adhesive particles and the above-mentioned binder, the above-mentioned adhesive may also contain, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a hardening catalyst, a colorant, an antioxidant, a heat stabilizer, Various additives such as light stabilizers, UV absorbers, lubricants, antistatic agents and flame retardants.

In 100% by weight of the above-mentioned adhesive, the content of the above-mentioned binder is preferably 10% by weight or more, more preferably 30% by weight or more, further preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably 99.99% by weight or less, more preferably 99.9% by weight or less. Adhesion can be further improved as content of the said binder is more than the said minimum and below the said upper limit.

In 100% by weight of the above-mentioned adhesive, the content of the above-mentioned adhesive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight or less, and more preferably It is 40% by weight or less, more preferably 20% by weight or less, and most preferably 10% by weight or less. Adhesion can be further improved as content of the said adhesive particle is more than the said minimum and below the said upper limit, and a clearance gap can be controlled with high precision.

<Light control laminate> The light-adjusting laminate of the present invention includes a first substrate, a second substrate, and a light-adjusting layer disposed between the first substrate and the second substrate. In the light-adjusting laminate of the present invention, the material of the light-adjusting layer contains the above-mentioned adhesive particles.

4 is a cross-sectional view showing an example of a PDLC-type light-adjusting laminate using the adhesive particles according to the first embodiment of the present invention.

The PDLC type light-adjusting laminate 51 includes a first substrate 52 , a second substrate 53 , and a light-adjusting layer 54 . The light adjustment layer 54 is arranged between the first substrate 52 and the second substrate 53 . Between the 1st board|substrate 52 and the 2nd board|substrate 53, a sealant can also be arrange|positioned around the light-adjusting layer 54.

The light-adjusting layer 54 includes liquid crystal capsules 54A, a binder 54B, and a plurality of adhesive particles 1 . The liquid crystal capsules 54A are dispersed in the binder 54B. The liquid crystal capsule 54A is held in the adhesive 54B in a capsule shape. The liquid crystal material can be dispersed in the adhesive in the form of capsules, and the liquid crystal material can also be dispersed in the adhesive in the form of a continuous phase.

The adhesive particle 1 is a spherical adhesive particle. In the PDLC-type light-adjusting laminate 51, the thermosetting resin portion of the adhesive particle 1 is thermally cured.

5 is a cross-sectional view showing an example of an SPD-type light-adjusting laminate using the adhesive particles according to the first embodiment of the present invention.

The SPD type light-adjusting laminate 61 includes a first substrate 62 , a second substrate 63 , and a light-adjusting layer 64 . The light adjustment layer 64 is arranged between the first substrate 62 and the second substrate 63 . Between the 1st board|substrate 62 and the 2nd board|substrate 63, a sealant can also be arrange|positioned around the light-adjusting layer 64.

The material of the light-adjusting layer 64 includes a plurality of adhesive particles 1 . The adhesive particle 1 is a spherical adhesive particle. In the SPD-type light-adjusting laminate 61, the thermosetting resin portion of the adhesive particle 1 is thermally cured.

The light-adjusting layer 64 includes droplets 64A of the light-adjusting suspension, and a resin matrix 64B. Droplets 64A of the light modulating suspension are dispersed in resin matrix 64B. The droplets 64A of the light-adjusting suspension are held in the resin matrix 64B in a droplet state.

The droplets 64A of the light-adjusting suspension include a dispersion medium 64Aa and light-adjusting particles 64Ab. The light adjustment particles 64Ab are dispersed in the dispersion medium 64Aa.

A transparent electrode can be formed on the surface of the said 1st board|substrate and the surface of the said 2nd board|substrate. As a material of the said transparent electrode, indium tin oxide (ITO) etc. are mentioned.

The above-mentioned light-adjusting layer has light-adjusting properties. The above-mentioned dimming property refers to the property that the transmittance of visible light changes depending on whether or not an electric field is applied, and the amount of incident light can be adjusted. As an action mechanism for changing the transmittance of visible light, for example, there are PDLC (Polymer Dispersed Liquid Crystal, polymer dispersed liquid crystal) method, SPD (Suspended Particle Device, suspended particle device) method, guest host liquid crystal method using liquid crystal, TN (Twisted liquid crystal) method Nematic, twisted nematic) method, VA (Vertical Alignment, vertical alignment) method, IPS (In-Plane-Switching, plane switching) method and the like. The material of the above-mentioned light-adjusting layer is not particularly limited, and any material may be used as long as it has light-adjusting properties.

The above-mentioned light-adjustable laminate is preferably a PDLC-type light-adjustable laminate or an SPD-type light-adjustable laminate.

[PDLC method] The above-mentioned light-adjusting layer preferably further comprises an adhesive and a liquid crystal material dispersed in the above-mentioned adhesive.

The above-mentioned liquid crystal material is not particularly limited. The above-mentioned liquid crystal material preferably has the property that the alignment is changed according to the application of an electric field. The above-mentioned liquid crystal material can be dispersed in the above-mentioned adhesive in the form of a continuous phase, or can be dispersed in the above-mentioned adhesive in the form of liquid crystal droplets or liquid crystal capsules. As said liquid crystal material, a nematic liquid crystal, a cholesteric liquid crystal, etc. are mentioned.

As a material of the said nematic liquid crystal, a cyanobiphenyl system, a phenyl ester system, an oxyazobenzene system, a fluorine-containing biphenyl system, a carbonate system, a Schiff base system, etc. are mentioned. Only one type of material for the above-mentioned nematic liquid crystal may be used, or two or more types may be used in combination.

Examples of the material of the cholesteric liquid crystal include steroid-based cholesterol derivatives, Schiff base-based, azo-based, oxyazo-based, benzoate-based, biphenyl-based, triphenyl-based, and cyclohexylcarboxyl Acid ester series, phenylcyclohexane series, biphenylcyclohexane series, pyrimidine series, diethane series, cyclohexylcyclohexane ester series, cyclohexylethane series, cyclohexane series, diphenylacetylene series, Nematic liquid crystals or smectic liquid crystals such as alkenyl-based, stilbene-based, condensed polycyclic liquid crystals, and optically active materials such as Schiff base-based, azo-based, ester-based, and biphenyl-based liquid crystals added to their mixed liquid crystals materials made of chiral molecules, etc. Only one type of the above-mentioned cholesteric liquid crystal material may be used, or two or more types may be used in combination.

The binder holds the liquid crystal material and suppresses the flow of the liquid crystal material. The above-mentioned binder is not particularly limited. The above-mentioned adhesive is preferably insoluble in the liquid crystal material, has the strength to withstand external force, and has high transmittance to reflected light and incident light. As the material of the above-mentioned binder, gelatin, polyvinyl alcohol, cellulose derivatives, polyacrylic acid-based polymers, ethyleneimine, polyethylene oxide, polyacrylamide, and polystyrene sulfonic acid may, for example, be mentioned. Water-soluble polymer materials such as salts, polyamidines, isoprene-based sulfonic acid polymers, etc., and water-based emulsifiable materials such as fluororesins, polysiloxanes, acrylic resins, urethane resins, and epoxy resins Wait. Only one type of the above-mentioned adhesive material may be used, or two or more types may be used in combination.

The above-mentioned adhesive is preferably cross-linked with a cross-linking agent. The above-mentioned crosslinking agent is not particularly limited. The above-mentioned cross-linking agent preferably forms a cross-link between the above-mentioned adhesives, so that the above-mentioned adhesive can be hardened, insoluble, or insolubilized. As said crosslinking agent, acetaldehyde, glutaraldehyde, glyoxal, aluminum potassium sulfate hydrate of polyvalent metal salt compound, adipic acid dihydrazine, melamine formalin oligomer, ethylene glycol, Diglycidyl ether, polyamide epichlorohydrin, and polycarbodiimide, etc. Only one type of the above-mentioned crosslinking agent may be used, or two or more types may be used in combination.

[SPD method] The light-adjusting layer preferably further includes a resin matrix and a light-adjusting suspension dispersed in the resin matrix.

The light-adjusting suspension described above includes a dispersion medium and light-adjusting particles dispersed in the dispersion medium.

Examples of the light-adjusting particles include carbon-based materials such as polyiodides and carbon black, metal materials such as copper, nickel, iron, cobalt, chromium, titanium, and aluminum, and silicon nitride, titanium nitride, and aluminum oxide. Inorganic compound materials, etc. Also, these materials may be polymer-coated particles. Only one type of the above-mentioned light-adjusting particles may be used, or two or more types may be used in combination.

The said dispersion medium disperse|distributes the said light adjustment particle in the state which can flow. The dispersion medium is preferably a material that selectively adheres to the light-adjusting particles, coats the light-adjusting particles, and acts when phase-separated from the resin matrix to move the light-adjusting particles to phase-separated droplets , no electrical conductivity, and no affinity with the resin matrix. Further, the dispersion medium is preferably a liquid copolymer having a refractive index similar to that of the resin matrix when the light-adjusting laminate is formed. As said liquid copolymer, the (meth)acrylate oligomer which has a fluorine group or a hydroxyl group is preferable, and the (meth)acrylate oligomer which has a fluorine group and a hydroxyl group is more preferable. If such a copolymer is used, the monomeric units of the fluorine group or the hydroxyl group are directed toward the light-adjusting particles, and the remaining monomeric units stabilize the droplets of the light-adjusting suspension in the resin matrix. Therefore, the light-adjusting particles are easily dispersed in the light-adjusting suspension, and the light-adjusting particles are easily guided into the phase-separated droplets when phase-separated from the resin matrix.

Examples of the (meth)acrylate oligomer having the above-mentioned fluorine group or hydroxyl group include 2,2,2-trifluoroethyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, acrylic acid 3,5,5-Trimethylhexyl/2-Hydroxypropyl Acrylate/Fumaric Acid Copolymer, Butyl Acrylate/2-Hydroxyethyl Acrylate Copolymer, 2,2,3,3-Tetraacrylate Fluoropropyl/butyl acrylate/2-hydroxyethyl acrylate copolymer, 1H,1H,5H-octafluoropentyl acrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, 1H,1H,2H,2H acrylate - Heptadecafluorodecyl/butyl acrylate/2-hydroxyethyl acrylate copolymer, 2,2,2-trifluoroethyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, methacrylic acid 2,2,3,3-Tetrafluoropropyl/butyl acrylate/2-hydroxyethyl acrylate copolymer, 1H,1H,5H-octafluoropentyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate Copolymer, and 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, etc. Moreover, it is more preferable that these (meth)acrylate oligomers have both a fluorine group and a hydroxyl group.

The weight average molecular weight of the (meth)acrylate oligomer is preferably 1,000 or more, more preferably 2,000 or more, preferably 20,000 or less, and more preferably 10,000 or less.

The light-adjusting layer can be produced using the resin material for forming the resin matrix and the light-adjusting suspension.

The above-mentioned resin material is preferably a resin material hardened by irradiating energy rays. As the resin material hardened by irradiation with energy rays, a polymer composition containing a photopolymerization initiator and a polymer compound hardened by energy rays such as ultraviolet rays, visible rays, and electron beams can be exemplified. As said polymer composition, the polymer composition containing the polymerizable monomer which has an ethylenically unsaturated group and a photopolymerization initiator is mentioned. As a polymerizable monomer which has the said ethylenically unsaturated group, a non-crosslinkable monomer and a crosslinkable monomer are mentioned.

Examples of the above-mentioned non-crosslinkable monomers include styrene monomers such as vinyl compounds, such as styrene, α-methylstyrene, and chlorostyrene; methyl vinyl ether, ethyl vinyl ether, propylene Vinyl ether compounds such as vinyl ether; vinyl acid compounds such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate; halogen-containing monomers such as vinyl chloride and vinyl fluoride; as (methyl) Acrylic compounds of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate ) Alkyl (meth)acrylates such as lauryl acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, iso(meth)acrylate, etc. Compounds; (meth)acrylates containing oxygen atoms such as 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, and glycidyl (meth)acrylate Compounds; nitrile-containing monomers such as (meth)acrylonitrile; (meth)acrylate compounds containing halogens such as trifluoromethyl (meth)acrylate and pentafluoroethyl (meth)acrylate; as α-olefin compounds Olefin compounds such as isobutylene, isobutylene, Linealene, ethylene, and propylene; as conjugated diene compounds, isoprene, butadiene, etc.

Examples of the above-mentioned crosslinkable monomers include vinyl-based monomers such as divinylbenzene, 1,4-divinyloxybutane, and divinyl as a vinyl-based compound; and as a (meth)acrylic compound Tetramethylolmethane tetra(meth)acrylate, polytetramethylene glycol diacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate , polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and other polyfunctional (Meth)acrylate compound; Triallyl (iso)cyanurate, triallyl trimellitate, diallyl phthalate, diallyl acrylamide, Diallyl ether; tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane as silane compounds , isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyl Trimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, trimethoxysilylstyrene, γ-(meth)acryloyloxy Silane alkoxide compounds such as propylpropyltrimethoxysilane, 1,3-divinyltetramethyldisiloxane, methylphenyldimethoxysilane, diphenyldimethoxysilane; vinyl Trimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, dimethoxyethylvinylsilane, diethoxymethylvinylsilane, diethoxyethylethylene Silane, Ethylmethyldivinylsilane, Methylvinyldimethoxysilane, Ethylvinyldimethoxysilane, Methylvinyldiethoxysilane, Ethylvinyldiethoxy Silane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxy Oxidation of silanes containing polymerizable double bonds, such as oxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and 3-acryloyloxypropyltrimethoxysilane cyclosiloxanes such as decamethylcyclopentasiloxane; modified (reactive) polysiloxanes such as single-end modified polysiloxane oil, double-end polysiloxane oil, and side-chain polysiloxane oil Oil; (meth)acrylic acid, maleic acid, maleic anhydride and other carboxyl-containing monomers, etc.

As the above-mentioned photopolymerization initiator, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-(4-(2-hydroxyethoxy)phenyl) )-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, and (1-hydroxycyclohexyl) phenyl ketone, etc.

The above-mentioned resin materials may include organic solvent-soluble resins, thermoplastic resins, poly(meth)acrylic acid, and the like. Moreover, the said resin material may contain various additives, such as an anti-coloring agent, an antioxidant, and an adhesiveness imparting agent, and may contain a solvent.

[SPD method] The light-adjusting layer preferably further includes a resin matrix and a light-adjusting suspension dispersed in the resin matrix.

The light-adjusting suspension described above includes a dispersion medium and light-adjusting particles dispersed in the dispersion medium.

Examples of the light-adjusting particles include carbon-based materials such as polyiodides and carbon black, metal materials such as copper, nickel, iron, cobalt, chromium, titanium, and aluminum, and silicon nitride, titanium nitride, and aluminum oxide. Inorganic compound materials, etc. In addition, these materials may also be particles obtained by coating with a polymer. Only one type of the above-mentioned light-adjusting particles may be used, or two or more types may be used in combination.

The said dispersion medium disperse|distributes the said light adjustment particle in the state which can flow. The dispersion medium is preferably a material that selectively adheres to the light-adjusting particles, coats the light-adjusting particles, and moves the light-adjusting particles to the phase-separated droplet phase when phase-separated from the resin matrix. It has no electrical conductivity and no affinity with the resin matrix. Furthermore, the dispersion medium is preferably a liquid copolymer having a refractive index similar to that of the resin matrix when the light-adjusting laminate is formed. As said liquid copolymer, the (meth)acrylate oligomer which has a fluorine group or a hydroxyl group is preferable, and the (meth)acrylate oligomer which has a fluorine group and a hydroxyl group is more preferable. If such a copolymer is used, the monomeric units of the fluorine group or the hydroxyl group are directed toward the light-adjusting particles, and the remaining monomeric units stabilize the droplets of the light-adjusting suspension in the resin matrix. Therefore, the light-adjusting particles are easily dispersed in the light-adjusting suspension, and the light-adjusting particles are easily guided into the phase-separated droplets when phase-separated from the resin matrix.

Examples of the (meth)acrylate oligomer having the above-mentioned fluorine group or hydroxyl group include 2,2,2-trifluoroethyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, acrylic acid 3,5,5-Trimethylhexyl/2-Hydroxypropyl Acrylate/Fumaric Acid Copolymer, Butyl Acrylate/2-Hydroxyethyl Acrylate Copolymer, 2,2,3,3-Tetraacrylate Fluoropropyl/butyl acrylate/2-hydroxyethyl acrylate copolymer, 1H,1H,5H-octafluoropentyl acrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, 1H,1H,2H,2H acrylate - Heptadecafluorodecyl/butyl acrylate/2-hydroxyethyl acrylate copolymer, 2,2,2-trifluoroethyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, methacrylic acid 2,2,3,3-Tetrafluoropropyl/butyl acrylate/2-hydroxyethyl acrylate copolymer, 1H,1H,5H-octafluoropentyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate Copolymer, and 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, etc. Moreover, it is more preferable that these (meth)acrylate oligomers have both a fluorine group and a hydroxyl group.

The weight average molecular weight of the (meth)acrylate oligomer is preferably 1,000 or more, more preferably 2,000 or more, preferably 20,000 or less, and more preferably 10,000 or less.

The light-adjusting layer can be produced using the resin material for forming the resin matrix and the light-adjusting suspension.

The above-mentioned resin material is preferably a resin material hardened by irradiating energy rays. As the resin material hardened by irradiation with energy rays, a polymer composition containing a photopolymerization initiator and a polymer compound hardened by energy rays such as ultraviolet rays, visible rays, and electron beams can be exemplified. As said polymer composition, the polymer composition containing the polymerizable monomer which has an ethylenically unsaturated group and a photopolymerization initiator is mentioned. As a polymerizable monomer which has the said ethylenically unsaturated group, a non-crosslinkable monomer and a crosslinkable monomer are mentioned.

Examples of the above-mentioned non-crosslinkable monomers include styrene monomers such as vinyl compounds, such as styrene, α-methylstyrene, and chlorostyrene; methyl vinyl ether, ethyl vinyl ether, propylene Vinyl ether compounds such as vinyl ether; vinyl acid compounds such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate; halogen-containing monomers such as vinyl chloride and vinyl fluoride; as (methyl) Acrylic compounds of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate ) Alkyl (meth)acrylates such as lauryl acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, iso(meth)acrylate, etc. Compounds; (meth)acrylates containing oxygen atoms such as 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, and glycidyl (meth)acrylate Compounds; nitrile-containing monomers such as (meth)acrylonitrile; (meth)acrylate compounds containing halogens such as trifluoromethyl (meth)acrylate and pentafluoroethyl (meth)acrylate; as α-olefin compounds Olefin compounds such as isobutylene, isobutylene, Linealene, ethylene, and propylene; as conjugated diene compounds, isoprene, butadiene, etc.

Examples of the above-mentioned crosslinkable monomers include vinyl-based monomers such as divinylbenzene, 1,4-divinyloxybutane, and divinyl as a vinyl-based compound; and as a (meth)acrylic compound Tetramethylolmethane tetra(meth)acrylate, polytetramethylene glycol diacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate , polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and other polyfunctional (Meth)acrylate compound; Triallyl (iso)cyanurate, triallyl trimellitate, diallyl phthalate, diallyl acrylamide, Diallyl ether; tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane as silane compounds , isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyl Trimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, trimethoxysilylstyrene, γ-(meth)acryloyloxy Silane alkoxide compounds such as propylpropyltrimethoxysilane, 1,3-divinyltetramethyldisiloxane, methylphenyldimethoxysilane, diphenyldimethoxysilane; vinyl Trimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, dimethoxyethylvinylsilane, diethoxymethylvinylsilane, diethoxyethylethylene Silane, Ethylmethyldivinylsilane, Methylvinyldimethoxysilane, Ethylvinyldimethoxysilane, Methylvinyldiethoxysilane, Ethylvinyldiethoxy Silane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxy Oxidation of silanes containing polymerizable double bonds, such as oxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and 3-acryloyloxypropyltrimethoxysilane cyclosiloxanes such as decamethylcyclopentasiloxane; modified (reactive) polysiloxanes such as single-end modified polysiloxane oil, double-end polysiloxane oil, and side-chain polysiloxane oil Oil; (meth)acrylic acid, maleic acid, maleic anhydride and other carboxyl-containing monomers, etc.

As the above-mentioned photopolymerization initiator, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-(4-(2-hydroxyethoxy)phenyl) )-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, and (1-hydroxycyclohexyl) phenyl ketone, etc.

The above-mentioned resin materials may include organic solvent-soluble resins, thermoplastic resins, poly(meth)acrylic acid, and the like. Moreover, the said resin material may contain various additives, such as an anti-coloring agent, an antioxidant, and an adhesiveness imparting agent, and may contain a solvent.

(1st board and 2nd board) It is preferable that the said 1st board|substrate and the said 2nd board|substrate are a board|substrate (translucent board|substrate) which has translucency. The first substrate and the second substrate are preferably transparent substrates. For example, light is transmitted from one side of the transparent substrate to the other side through the transparent substrate. For example, when the substance on the other side is observed from one side of the transparent substrate through the transparent substrate, the substance can be observed. Transparency also includes translucency. The transparent substrate may be colorless and transparent, or may be colored and transparent.

The material of the said 1st board|substrate and the said 2nd board|substrate is not specifically limited. The material of the above-mentioned first substrate and the material of the above-mentioned second substrate may be the same or different. As a material of the said board|substrate, glass, a resin film, etc. are mentioned. Examples of the above-mentioned glass include soda lime glass, lead glass, borosilicate glass for general construction, and glass of various compositions for other applications, as well as functions such as heat-reflecting glass, heat-absorbing glass, and tempered glass. Glass. As said resin film, resin films, such as polyester films, such as polyethylene terephthalate, polyolefin films, such as polypropylene, and acrylic resin-type films, are mentioned. The above-mentioned transparent substrate is preferably a resin substrate, more preferably a resin film, and still more preferably a polyethylene terephthalate film, from the viewpoint of being excellent in transparency, moldability, adhesiveness, workability, and the like.

The first substrate and the second substrate preferably include a substrate body and a transparent conductive film formed on the surface of the substrate body so that an electric field for dimming can be applied. As said transparent conductive film, indium tin _oxide (ITO), _SnO2 , _In2O3 , etc. are mentioned.

From the viewpoint of improving the visibility of the light-adjustable laminate, the visible light transmittances of the first substrate and the second substrate are preferably 75% or more, more preferably 80% or more.

About the visible light transmittance of the said board|substrate, a spectroscopic measurement etc. can be implemented, and it can measure based on ISO13837:2008. Moreover, you may measure by the method etc. based on JISK6714 standard.

Hereinafter, an Example and a comparative example are given and this invention is demonstrated concretely. The present invention is not limited to the following examples.

Prepare the following materials.

Thermosetting resin: Thermosetting resin A (bisphenol A epoxy resin, "EXA-850-CRP" manufactured by DIC Corporation) Thermosetting resin B (bisphenol A epoxy resin, "EXA-4850-150" manufactured by DIC Corporation) Thermosetting resin C (1,12-dodecanediol diglycidyl ether, "DOD-DEP" manufactured by Yokkaichi Gosei Co., Ltd.)

hardener: Amine hardener (2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane)

Inorganic oxide particles: Silicon oxide dispersion ("TOL-ST" manufactured by Nissan Chemical Co., Ltd., average particle size 12 nm, 40 wt% dispersion of silicon oxide particles in toluene) Titanium dioxide powder ("Super Titania F-6A" manufactured by Showa Denko Co., Ltd., average particle size 15 nm)

Substrate particles: Substrate particle D ("Micropearl SP-209" manufactured by Sekisui Chemical Industry Co., Ltd., average particle size 9.0 μm, CV value 5%) Substrate particle E ("Micropearl KBN-509" manufactured by Sekisui Chemical Industry Co., Ltd., average particle size 9.0 μm, CV value 4%)

(Example 1) (1) Production of adhesive particles In a separable flask, 47 parts by weight of thermosetting resin A, 47 parts by weight of thermosetting resin B, 6 parts by weight of thermosetting resin C, polyvinylpyrrolidone ("K-30" manufactured by FUJIFILM Wako Pure Chemical Co., Ltd. ) 50 parts by weight, 16.6 parts by weight of cetyl ammonium bromide, and 1670 parts by weight of methanol were dissolved by mixing, and then 6.6 parts by weight of an amine hardener was added. After making it react at 45 degreeC for 10 hours, the silicon oxide dispersion liquid was added so that a silicon oxide particle might become 2.9 weight part, and it was made to react at 45 degreeC for 10 hours. Then, the mother liquor was separated, washed with methanol, and then dried under vacuum at 25° C. for 24 hours to obtain adhesive particles in which inorganic oxide particles were dispersed in the particle body (thermosetting resin portion).

(2) Fabrication of PDLC Mode Light-adjusting Laminate A PET film with a thickness of 50 μm was prepared as the material of the first substrate and the second substrate. An acrylic hard coat resin (“Lioduras TYZ” manufactured by Toyo Ink Co., Ltd.) in which zirconia particles are dispersed is applied to one side of a PET film, and then cured by irradiating UV (Ultraviolet) to form a thickness of 0.8 The first hard coat layer of μm. After applying an acrylic hard coat resin (“Lioduras TYAB” manufactured by Toyo Ink Co., Ltd.) on the other side of the PET film, it was cured by UV irradiation to form a second hard coat layer with a thickness of 2.0 μm. Thereby, a base film was obtained.

This base film was installed in a vacuum apparatus, and vacuum evacuation was performed. After the vacuum degree reaches 9.0×10 ^{- 4} Pa, argon gas is introduced, and the first hard coat layer is removed from the first hard coat layer on the surface of the first hard coat layer by DC (direct current, direct current) magnetron sputtering method in an argon atmosphere. A SiO _x layer, a SiO ₂ layer and a SiO _x layer are sequentially formed from the side, and an indium tin oxide (ITO) layer is laminated on the layers. Specifically, an ITO sintered body target with SnO ₂ of 7 wt % was used, and a cathode whose maximum horizontal magnetic flux density on the surface of the target was 1000 Gauss was used under the chamber pressure of 3.5×10 ^-1 Pa. Ar gas was mixed with Ar gas. The ratio of the O ₂ gas was set to 100:1, and then a conductive layer (indium tin oxide layer) with a thickness of 18 nm was formed while introducing it into a vacuum apparatus. Then, annealing treatment was performed at 160° C. for 9 minutes in an IR (Infrared) heating oven (manufactured by MINO GROUP) to obtain a first substrate and a second substrate (substrate of a transparent conductive film). Adhesive particles were scattered on the surface of the first substrate so as to be 15 particles/cm ² . Next, a light-adjusting material (produced according to the method described in "Macromolecules", Vol. 26, pp. 6132-6134 (1993)) is laminated, and a second substrate is laminated. At this time, it heated at 120 degreeC for 100 minutes under the pressure of 2 kgf/cm< ² >, and adhered the adhesive particle on the 1st, 2nd board|substrate, and produced the light control laminated body.

(Examples 2 to 5 and Comparative Example 1) Adhesive particles and a light-adjustable laminate were produced in the same manner as in Example 1, except that the blending amounts of the thermosetting resin and the inorganic oxide particles were changed as shown in Tables 1 and 2.

(Example 6) In a separable flask, 125 parts by weight of substrate particles D, 75 parts by weight of thermosetting resin A, 25 parts by weight of thermosetting resin B, and polyvinylpyrrolidone ("K-30" manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.) were prepared. After 312.5 parts by weight, 62.5 parts by weight of cetyltrimethylammonium bromide, and 12,500 parts by weight of methanol were dissolved by mixing, 12.5 parts by weight of an amine hardener was added. After making it react at 45 degreeC for 10 hours, the silicon oxide dispersion liquid was added so that a silicon oxide particle might become 7.1 weight part, and it was made to react at 45 degreeC for 10 hours further. Then, the mother liquor was separated, washed with methanol, and then dried under vacuum at 25° C. for 24 hours to obtain substrate particles whose surfaces were covered with a thermosetting resin portion, and the covering portion (thermosetting resin portion) dispersed with Adhesive particles of inorganic oxide particles. A light-adjusting laminate was produced in the same manner as in Example 1, except that the obtained adhesive particles were used.

(Example 7) Adhesive particles and a light-adjusting laminate were produced in the same manner as in Example 6, except that the base particles D were changed to the base particles E.

(Comparative Example 2) To the separable flask, 10 parts by weight of base material particles D, 100 parts by weight of methanol, and 900 parts by weight of ion-exchanged water in which 1.5% by weight of sodium p-styrenesulfonate was dissolved were added and sufficiently dispersed. Then, a solution obtained by dissolving 10 parts by weight of styrene monomer, 1 part by weight of silicon oxide particles, and 0.1 part by weight of ammonium peroxodisulfate in 30 parts by weight of ion-exchanged water was added, and the mixture was added to 70 parts by weight. The reaction was carried out at °C for 10 hours. Then, the mother liquor was separated, washed with ion-exchanged water, and then dried under reduced pressure at 55° C. for 24 hours, thereby producing particles having no thermosetting resin portion and the surfaces of the substrate particles being covered with a thermoplastic resin. A light-adjusting laminate was produced in the same manner as in Example 1, except that the obtained particles were used.

(Evaluation) (1) Cohesion (single particle rate) The cross section of the adhesive particle was cut out using an ion milling apparatus (“IM4000” manufactured by Hitachi High-Technology Co., Ltd.) so as to pass through the vicinity of the center of the adhesive particle in the obtained light-adjusting laminate. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification was set to 800 times, and 10 fields of view were randomly selected to observe the adhesive particles. The ratio (%) of the number of unagglomerated adhesive particles to the total number of adhesive particles was taken as the single particle rate. Furthermore, the higher the single particle rate, the lower the cohesiveness of the particles.

(2) Ejection The obtained adhesive particles and epoxy resin (“jER828” manufactured by Mitsubishi Chemical Co., Ltd.) were filled in a syringe and defoamed to obtain an adhesive. Using a dispenser (“SHOTMASTER300” manufactured by Musang Hi-Tech Co., Ltd.), under the conditions of drawing speed 50 mm/min, ejection pressure 0.2 MPa, and nozzle diameter 0.25 mm, the obtained adhesive was ejected by 5 cm. The clogging of the adhesive particles at this time was confirmed. The ejectability was determined according to the following criteria.

[Judgment criteria for ejectability] ○○: 5 cm can be ejected without clogging ○: 3 cm or more and less than 5 cm can be ejected without clogging ×: Less than 3 cm, clogging occurred

(3) Damage resistance during ejection The adhesive particles after the above-mentioned ejectability test were observed using a digital microscope (“VHX-2000” manufactured by Keyence Corporation) to observe whether or not the particles were damaged. The image magnification was set to 200 times, and 500 arbitrary adhesive particles were observed. The damage resistance at the time of ejection of adhesive particles was determined according to the following criteria.

[Judgment criteria for damage resistance during ejection] ○○: The number of broken adhesive particles is less than 5 ○: The number of broken adhesive particles is 5 or more and less than 20 ×: 20 or more broken adhesive particles

(4) Liquid drop suppression property The above-mentioned transparent conductive film was prepared as a 1st board|substrate and a 2nd board|substrate. On the surface of the 1st board|substrate, the obtained adhesive particle was spread|dispersed so that it might become 15 pieces/cm< ² >. Next, the second substrate is laminated. Then, it heated at 180 degreeC for 40 minutes, and observed whether dripping occurred on the particle surface using a digital microscope ("VHX-2000" by Keyence Corporation). The image magnification was set to 200 times, and 50 arbitrary adhesive particles were observed. The drip suppression property was judged based on the following criteria.

[Judgment criteria for drip inhibition] ○○: Less than 5 adhesive particles with dripping ○: There are 5 or more and less than 15 adhesive particles with dripping △: 15 or more and less than 30 adhesive particles with dripping ×: There are 30 or more adhesive particles in which dripping occurs

(5) Adhesion (tensile yield stress) Using the obtained adhesive particles, a test body (test sample) was produced according to the above-mentioned adhesive test A. The tensile yield stress at 23° C. of the above-mentioned test body was measured using a Tensilon universal testing machine (“RTI-1310” manufactured by A&D Corporation) (adhesion test A). Adhesion was determined according to the following criteria.

[Judgment Criteria for Adhesion] ○○: Tensile yield stress is 0.12 MPa or more ○: Tensile yield stress is 0.07 MPa or more and less than 0.12 MPa ×: Tensile yield stress less than 0.07 MPa

The structures and results of the adhesive particles are shown in Tables 1 and 2 below.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Adhesive particles shape - figure 1 figure 1 figure 1 figure 1 figure 1 Thermosetting resin A content parts by weight 47 47 47 75 47 Thermosetting resin B content parts by weight 47 47 47 25 47 Thermosetting resin C content parts by weight 6 6 6 0 6 Inorganic oxide particles type - Silicon oxide Silicon oxide Silicon oxide Silicon oxide Titanium dioxide content parts by weight 2.9 6.3 0.7 2.9 2.6 Substrate particles type - - - - - - particle size μm 0 0 0 0 0 particle size μm 12.3 10.9 11.5 14.8 12.9 Evaluation Cohesion (single particle rate) % 97 98.0 89 98 91 squirting sex - ○○ ○○ ○ ○○ ○ Damage resistance when ejected - ○○ ○○ ○ ○○ ○ drip inhibition - ○○ ○○ △ ○○ ○ continuity - ○○ ○ ○○ ○ ○○

[Table 2] Example 6 Example 7 Comparative Example 1 Comparative Example 2 Adhesive particles shape - figure 2 figure 2 - - Thermosetting resin A content parts by weight 75 75 47 0 Thermosetting resin B content parts by weight 25 25 47 0 Thermosetting resin C content parts by weight 0 0 6 0 Inorganic oxide particles type - Silicon oxide Silicon oxide - Silicon oxide content parts by weight 7.1 7.6 0.0 1.0 Substrate particles type - D E - D particle size μm 9.0 9.0 0 9.0 particle size μm 15.6 16.4 11.0 10.0 Evaluation Cohesion (single particle rate) % 97 97 6 98 squirting sex - ○○ ○○ × ○○ Damage resistance when ejected - ○ ○ ○ × drip inhibition - ○○ ○○ × × continuity - ○ ○ ○○ ×

1: Adhesive particles 2: Particle body (thermosetting resin part) 3: Inorganic oxide particles 11: Adhesive Particles 12: Coating part (coating layer) 13: Inorganic oxide particles 14: Substrate particles 21: Adhesive Particles 22: Coating part (plurality of particles) 23: Inorganic oxide particles 24: Substrate particles 51: PDLC mode dimming laminate 52: The first substrate 53: Second substrate 54: Dimming layer 54A: Liquid crystal capsule 54B: Adhesive 61: SPD mode dimming laminated body 62: 1st substrate 63: Second substrate 64: Dimming layer 64A: Droplets of Light Adjusting Suspension 64Aa: dispersion medium 64Ab: Light Tuning Particles 64B: resin matrix

FIG. 1 is a cross-sectional view showing an adhesive particle according to a first embodiment of the present invention. FIG. 2 is a cross-sectional view showing an adhesive particle according to a second embodiment of the present invention. 3 is a cross-sectional view showing an adhesive particle according to a third embodiment of the present invention. 4 is a cross-sectional view showing an example of a PDLC-type light-adjusting laminate using the adhesive particles according to the first embodiment of the present invention. 5 is a cross-sectional view showing an example of an SPD-type light-adjusting laminate using the adhesive particles according to the first embodiment of the present invention.

Claims (7)

An adhesive particle comprising a thermosetting resin portion and a plurality of inorganic oxide particles, and The said inorganic oxide particle is dispersed in the said thermosetting resin part, or the said inorganic oxide particle is attached to the surface of the said thermosetting resin part. The adhesive particle according to claim 1, wherein the inorganic oxide particle is silicon oxide. The adhesive particle of Claim 1 or 2 whose thermosetting resin of the said thermosetting resin part is an epoxy resin. The adhesive particles of claim 1 or 2, wherein the adhesive particles have substrate particles inside, The said base material particle contains a thermoplastic resin. The adhesive particle according to claim 4, wherein the base material particle contains a pigment or a dye. An adhesive comprising the adhesive particles as claimed in any one of claims 1 to 5, and adhesive. A light-adjusting laminate comprising a first substrate, a second substrate, and a light-adjusting layer disposed between the first substrate and the second substrate, and The material of the above-mentioned light-adjusting layer includes the adhesive particles according to any one of claims 1 to 5.

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