CN116583407A

CN116583407A - Adhesive particle, adhesive, and light control laminate

Info

Publication number: CN116583407A
Application number: CN202180084077.XA
Authority: CN
Inventors: 山田恭幸; 胁屋武司; 小林洋
Original assignee: Sekisui Chemical Co Ltd
Current assignee: Sekisui Chemical Co Ltd
Priority date: 2020-12-16
Filing date: 2021-12-16
Publication date: 2023-08-11
Also published as: JPWO2022131318A1; WO2022131318A1; TW202233788A

Abstract

The invention provides adhesive particles which can improve adhesion, effectively inhibit aggregation and inhibit dripping during heating. The adhesive particle of the present invention comprises 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 adhered to the surface of the thermosetting resin portion.

Description

Adhesive particle, adhesive, and light control laminate

Technical Field

The present invention relates to adhesive particles. The present invention also relates to an adhesive and a light control laminate using the adhesive particles.

Background

Dimming materials such as dimming glass and a dimming film are sometimes used in display devices such as liquid crystal display devices and in-vehicle displays. The light control material has a property that the light transmittance changes according to the presence or absence of an applied electric field, and is a material capable of controlling the amount of incident light.

The liquid crystal display element is formed by disposing liquid crystal between 2 glass sheets or film substrates. In this liquid crystal display element, an adhesive is used for bonding 2 glass sheets or film substrates.

In recent years, with the increase in screen size and flexibility of display devices, there has been an increasing demand for adhesives having higher adhesion. In order to further improve the adhesiveness of the adhesive, particles having adhesiveness (adhesive particles) may be contained in the adhesive.

Patent document 1 discloses a thermosetting resin coated particle comprising spherical core particles having a hydrophobic substituent introduced into the surface thereof, and a thermosetting resin layer coating the surface of the core particles with the hydrophobic substituent interposed therebetween. The thermosetting resin coated particles can be used for liquid crystal display devices. The thermosetting resin layer contains a radical polymerizable acrylate prepolymer having a softening point of 40 to 150 ℃ and a radical polymerization initiator that generates radicals by heating to a temperature of 60 to 150 ℃. In patent document 1, a method (hybridization method) is used in which core particles and microparticles coating the surfaces of the core particles are caused to collide with each other in a high-speed air stream, and a resin layer is formed on the surfaces of the core particles by the heat of the collision.

Patent document 2 below discloses an adhesive spacer for a liquid crystal display device, which includes seed particles and an adhesive layer derived from adhesive fine particles. The adhesive layer coats the surface of the seed particles. The adhesive fine particles are polymer particles containing 0.1 wt% or more and less than 50 wt% of constituent components derived from a specific polymerizable monomer having a long-chain alkyl group.

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

Disclosure of Invention

Technical problem to be solved by the invention

In the particles formed by the hybridization method as in patent document 1, there are the following problems: the adhesion force between the core particles and the resin layer is insufficient, and the resin layer is easily peeled from the core particles. In addition, when the particles are heated, the thermosetting resin on the surfaces of the particles melts to generate droplets, and as a result, the adhesiveness may be lowered.

In the conventional adhesive spacer described in patent document 2, there are cases where the adhesive fine particles are aggregated with each other. As a result, when the adhesive spacer is applied to a substrate or the like by a dispenser or the like, the nozzle may be clogged or the adhesive spacer may be broken by collision with the substrate.

The purpose of the present invention is to provide adhesive particles which can improve adhesion, effectively inhibit aggregation, and inhibit dripping during heating. The present invention also provides an adhesive and a light control laminate using the adhesive particles.

Technical means for solving the technical problems

According to a broad 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 adhered to the surface of the thermosetting resin portion.

In a specific aspect of the adhesive particle of the present invention, the inorganic oxide particle is silica.

In a specific aspect of the adhesive particle of the present invention, the thermosetting resin of the thermosetting resin part is an epoxy resin.

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

In a specific aspect of the adhesive particle of the present invention, the substrate particle comprises a pigment or a dye.

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

According to a broad aspect of the present invention, there is provided a light control laminate comprising a 1 st substrate, a 2 nd substrate, and a light control layer disposed between the 1 st substrate and the 2 nd substrate, wherein a material of the light control layer contains the adhesive particles.

Effects of the invention

The adhesive particle of the present invention comprises 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 adhered to the surface of the thermosetting resin portion. In the adhesive particle of the present invention, since the above-described structure is provided, the adhesion can be improved, aggregation can be effectively suppressed, and dripping during heating can be suppressed.

Drawings

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 adhesive particles according to a second embodiment of the present invention.

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

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

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

Detailed Description

The following describes the details of the present invention.

< adhesive particle >)

The adhesive particle of the present invention comprises a thermosetting resin portion and a plurality of inorganic oxide particles. In the adhesive particle of the present invention, the inorganic oxide particles are dispersed in the thermosetting resin portion or the inorganic oxide particles are adhered to the surface of the thermosetting resin portion. In the adhesive particles, the inorganic oxide particles may be dispersed in the thermosetting resin portion, and the inorganic oxide particles may be adhered to the surface of the thermosetting resin portion. In order to further improve the adhesion and to further effectively prevent breakage due to collision with the substrate during application, it is preferable that the inorganic oxide particles are dispersed in the thermosetting resin portion.

In the adhesive particle of the present invention, the above-described structure is provided, so that aggregation can be effectively suppressed. As a result, the ejection property of the ink applied to a substrate or the like by a dispenser or the like can be improved. Specifically, nozzle clogging at the time of coating can be made less likely to occur. Further, the particles can be prevented from being broken by collision with the substrate.

In addition, since the adhesive particle of the present invention has the above-described structure, the adhesion can be improved. In the adhesive particle of the present invention, the thermosetting resin portion is thermally cured to enable adhesion.

Further, since the adhesive particle of the present invention has the above-described configuration, dripping caused by melting of the thermosetting resin portion during heating can be suppressed, and adhesion can be maintained at a high level. In addition, contamination by dripping can be prevented.

The adhesive particles may be suitable for use in adhesives. The adhesive particles can be used for a light control material, a light control layer, and a light control laminate. The adhesive particles may be used as spacers for light control glass or spacers for light control film. The adhesive particle may be an adhesive particle for a light control laminate.

The shape of the adhesive particle is not particularly limited. The shape of the adhesive particle may be spherical, may be other than spherical, or may be flat. The spherical shape is not limited to a regular spherical shape, and includes a substantially spherical shape, and includes a shape having an aspect ratio (long diameter/short diameter) of 1.5 or less, for example.

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 main body 2 (thermosetting resin part). The particle body 2 (thermosetting resin portion) is formed of a thermosetting resin and includes 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 a base particle 14, a coating portion 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 particles 11 have base particles 14 inside. In the adhesive particle 11, the coating portion 12 contacts the surface of the base particle 14, and coats the surface of the base particle 14. The adhesive particles 11 are coated particles in which the surface of the base particles 14 is coated with the coating portion 12. In the adhesive particle 11, the coating portion 12 is a single-layer coating layer. In the adhesive particle 11, the coating portion 12 is a thermosetting resin portion. The thermosetting resin part is formed of a thermosetting resin and contains a thermosetting resin.

The adhesive particle 1 shown in fig. 1 and the adhesive particle 11 shown in fig. 2 are mainly different from the base particle 14. That is, the adhesive particles 1 do not have the base particles, but the adhesive particles 11 have the base particles 14.

The adhesive particle 21 shown in fig. 3 includes a base particle 24, a coating portion 22, and a plurality of inorganic oxide particles 23. In the adhesive particles 21, the inorganic oxide particles 23 are attached 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 contacts the surface of the base particle 24, and coats the surface of the base particle 24. The adhesive particles 21 are coated particles in which the surface of the base particles 24 is coated with the coating portion 22. In the adhesive particle 21, the coating portion 22 is formed of a plurality of particles. In the adhesive particle 21, the coating portion 22 includes a thermosetting resin portion. In the adhesive particles 21, particles forming the coating portion 22 include a thermosetting resin.

The adhesive particles 11 and the adhesive particles 21 are mainly different from the coating portions 12 and 22. That is, in the adhesive particle 11, the coating portion is a single-layer coating layer, whereas in the adhesive particle 21, the coating portion is formed of a plurality of particles. In the adhesive particles 1 and 11, the inorganic oxide particles are dispersed in the thermosetting resin, whereas in the adhesive particles 21, the inorganic oxide particles are adhered to the surface of the thermosetting resin portion.

The adhesive particles 11 and 21 have the base particles 14 and 24, and therefore have excellent gap controllability. Therefore, the adhesive particles 11 and 21 can be suitably used as spacers for a light control laminate or the like. The adhesive particles 11 and 21 can be suitably used as spacers for light control glass and spacers for light control film. For example, in the light control laminate in which the adhesive particles are arranged between the substrates, the gap between the substrates can be controlled with high accuracy, and the uniformity of the thickness between the substrates can be improved. Further, by suppressing peeling of the conductive film, the light adjusting performance of the light adjusting laminate can be maintained.

The surface area (coating ratio) of the coating portion is preferably 20% or more, more preferably 50% or more, still more preferably 80% or more, and particularly preferably 85% or more, of the total surface area of the base particles 100%. The upper limit of the coating ratio is not particularly limited. The coating ratio may be 100% or less, or 99% or less. When the coating ratio is not less than the lower limit, the adhesion can be further improved. In addition, when the adhesive particles are used as a gap material, the gap can be controlled with higher accuracy.

The surface area (coating ratio) of the substrate particles coated with the coating portion was determined by the following method of 100% of the total surface area: the adhesive particles were observed with an electron microscope or an optical microscope, and the percentage of the surface area covered with the covering portion relative to the projected area of the base material particles was calculated.

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, more preferably 7 μm or less, further preferably 5 μm or less, from the viewpoint of further improving the adhesiveness. In the case where the coating portion is formed of a plurality of layers, the thickness of the coating portion refers to the thickness of the entire coating portion.

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

The CV value of the particle diameter of the adhesive particles is preferably 10% or less, more preferably 7% or less, from the viewpoint of further improving the adhesion. The upper limit of the CV value of the particle diameter of the adhesive particle is not particularly limited. The adhesive particles may have a CV value of 30% or less in particle diameter.

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

CV value (%) = (ρ/Dn) ×100

ρ: standard deviation of particle diameter of the adhesive particle

Dn: average value of particle diameters of the adhesive particles

The adhesive particles preferably have a compression elastic modulus (10% K value) of 10N/mm when compressed at 25 ℃ by 10% ² The above is more preferably 1000N/mm ² Above, preferably 10000N/mm ² Hereinafter, more preferably 7000N/mm ² The following is given. If the 10% k value is not less than the lower limit and not more than the upper limit, the gap can be controlled with high accuracy.

The adhesive particles preferably have a compression elastic modulus (30% K value) of 50N/mm when compressed at 25℃by 30% ² The above is more preferably 2000N/mm ² Above, preferably 20000N/mm ² Hereinafter, 10000N/mm is more preferable ² The following is given. If the 30% k value is not less than the lower limit and not more than the upper limit, the gap can be controlled with high accuracy.

The compressive elastic modulus (10% k value and 30% k value) of the adhesive particle can be determined as follows.

1 adhesive particle was compressed using a micro compression tester at a smooth indenter end face of a cylinder (diameter 100 μm, made of diamond) under conditions of 25℃and a compression speed of 0.3 mN/sec and a maximum test load of 20 mN. The load value (N) and the compression displacement (mm) at this time were measured. The compressive elastic modulus (10% k value and 30% k value) can be obtained from the obtained measurement value by the following formula. For example, "FISCHERCOPE H-100" manufactured by FISCHER is used as the micro-compression tester. The compressive elastic modulus (10% k value and 30% k value) of the adhesive particle is preferably calculated by arithmetically averaging the compressive elastic moduli (10% k value and 30% k value) of 50 adhesive particles arbitrarily selected.

10% K value and 30% K value (N/mm ² )＝(3/2 ^1/2 )·F·S ^-3/2 ·R ^-1/2

F: load value (N) at 10% or 30% compression deformation of adhesive particle

S: compressive displacement (mm) when the adhesive particles are deformed by 10% or 30% in compression

R: radius (mm) of adhesive particle

The compressive elastic modulus generally and quantitatively represents the hardness of the adhesive particle. By using the compressive elastic modulus, the hardness of the adhesive particle can be quantitatively and unambiguously expressed.

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

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

(adhesion test A)

As the 1 st substrate and the 2 nd substrate, glass substrates were prepared. 10 pieces/mm on the surface of the 1 st substrate ² Is dispersed with adhesive particles. Next, the temperature was set to 5kgf/cm in accordance with JIS K6850 ² The mixture was heated at 100℃for 60 minutes to bond the adhesive particles to the 1 st and 2 nd substrates, thereby preparing a test body (test sample). The adhesion strength of the test body obtained was measured at 23℃using a TENSILON universal material tester at a tensile speed of 20mm/min and a load cell rating of 1000N. The measured value was used as the tensile yield stress of the adhesive particle.

(adhesion test B)

As the 1 st substrate and the 2 nd substrate, glass substrates were prepared. 10 pieces/mm on the surface of the 1 st substrate ² Is dispersed with adhesive particles. Next, the temperature was set to 5kgf/cm in accordance with JIS K6850 ² The mixture was heated at 130℃for 60 minutes to bond the adhesive particles to the 1 st and 2 nd substrates, thereby preparing a test body (test sample). The adhesion strength of the test body obtained was measured at 23℃using a TENSILON universal material tester at a tensile speed of 20mm/min and a load cell rating of 1000N. The measured value was used as the tensile yield stress of the adhesive particle.

As the glass substrate, S-7213 manufactured by Song Nitro industries, inc. or the like is used. As the TE NSILON universal material tester, "RTI-1310" manufactured by A & D company, etc. was used.

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

(thermosetting resin part/thermosetting resin)

In the adhesive particle of the present invention, the particle body of the adhesive particle may contain a thermosetting resin portion, the particle body of the adhesive particle may be a thermosetting resin portion, the coating portion in contact with the surface of the base particle may contain a thermosetting resin portion, and the coating portion may be a thermosetting resin portion. In the adhesive particle of the present invention, the particle main body of the adhesive particle is preferably a thermosetting resin part. In the adhesive particle of the present invention, the coating portion in contact with the surface of the base particle is preferably a thermosetting resin portion. The thermosetting resin portion may constitute a particle body of the adhesive particle, or may constitute a coating portion that contacts the surface of the base particle. The thermosetting resin part is formed of a thermosetting resin and contains a thermosetting resin. The thermosetting resin portion may contain components other than the thermosetting resin within a range that does not impair thermosetting properties. The component other than the thermosetting resin may be a resin.

The cladding may be formed of 1 layer. The cladding may also be formed from multiple layers. That is, the coating portion may have a laminated structure of 2 or more layers. In the case where the coating portion is formed of a plurality of layers, the outermost layer preferably contains a thermosetting resin portion. The coating may be formed of a plurality of particles. The coating portion is preferably a single-layer coating layer from the viewpoint of suppressing peeling of the coating portion from the surface of the base material particle.

Examples of the thermosetting resin include epoxy resins, vinyl ester resins, and unsaturated polyester resins. The thermosetting resin may be used alone or in combination of 1 or more than 2.

Examples of the epoxy resin include: bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, biphenyl novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, an epoxy resin having an adamantane skeleton, an epoxy resin having a tricyclodecane skeleton, an epoxy resin having a triazine core in the skeleton, and the like.

Examples of the vinyl ester resin include Bis (ethylene glycol) vinyl ester resins and novolak vinyl ester resins.

Examples of the unsaturated polyester resin include resins obtained by polycondensation of an α, β -unsaturated dicarboxylic acid or an anhydride thereof with a diol.

The thermosetting resin preferably contains an epoxy resin from the viewpoint of further improving the adhesion. The thermosetting resin is preferably an epoxy resin from the viewpoint of further improving the adhesion.

In the case of using an epoxy resin as a material of the adhesive particles, the epoxy resin is preferably a multifunctional epoxy resin. Examples of the polyfunctional epoxy resin include 2-functional epoxy resins such as bisphenol a type epoxy resin and bisphenol F type epoxy resin, 3-functional epoxy resins such as triazine type epoxy resin and glycidylamine type epoxy resin, and 4-functional epoxy resins such as tetraphenolethane type epoxy resin and glycidylamine type epoxy resin. The epoxy resin may be used in an amount of 1 or 2 or more.

In the case of using an epoxy resin as the material of the adhesive particles, a curing agent is preferably used together with the epoxy resin. The curing agent thermally cures the epoxy resin. The curing agent is not particularly limited. Examples of the curing agent include thiol curing agents such as imidazole curing agents, amine curing agents, phenol curing agents and polythiol curing agents, and acid anhydride curing agents. The curing agent may be used alone or in combination of 1 or more than 2. The curing agent is preferably an amine curing agent from the viewpoint of easily controlling the compression characteristics of the adhesive particles in an appropriate range.

The imidazole curing agent is not particularly limited. Examples of the imidazole curing agent include: an imidazole compound in which a 5-hydrogen atom of 1H-imidazole in 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine and 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine isocyanurate adduct, 2-phenyl-4, 5-dimethylol, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2-p-tolyl-4-methyl-5-hydroxymethylimidazole, 2-m-tolyl-4, 5-dimethylol imidazole, 2-p-tolyl-4, 5-dimethylol imidazole or the like is substituted with a hydroxymethyl group and a 2-position hydrogen atom is substituted with a phenyl group or a tolyl group, and the like.

The thiol curing agent is not particularly limited. Examples of the thiol curing agent include: trimethylolpropane tri-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate, and the like.

The amine curing agent is not particularly limited. The amine curing agent may be: 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-bis [4- (4-aminophenoxy) phenyl ] propane, metaphenylene diamine, diaminodiphenylmethane, diaminophenyl ether, metaxylene diamine, diaminonaphthalene, diaminomethylcyclohexane, diaminodiphenyl sulfone, and the like. The amine curing agent is preferably ethylenediamine, hexamethylenediamine, octamethylenediamine, 2,5 (2, 6) -bis (aminomethyl) bicyclo [2.2.1] heptane, metaphenylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, phenylenediamine or 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane. By using these preferred amine curing agents, the compression characteristics of the adhesive particles can be easily controlled within a suitable range. The amine curing agent 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, from the viewpoint of easily controlling the compression characteristics of the adhesive particles in an appropriate range.

The acid anhydride curing agent is not particularly limited, and may be widely used as long as it is an acid anhydride used as a curing agent for a thermosetting compound such as an epoxy compound. The acid anhydride curing agent may be: phthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylbutyltetrahydrophthalic anhydride, phthalic anhydride of a phthalic acid derivative, maleic anhydride, nadic anhydride, methylnadic anhydride, glutaric anhydride, succinic anhydride, glycerol bis-trimellitic anhydride monoacetate, ethylene glycol bis-trimellitic anhydride and other 2-functional acid anhydride curing agents, trimellitic anhydride and other 3-functional acid anhydride curing agents, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, polyazelaic anhydride and other 4-functional acid anhydride curing agents and the like.

The content of the thermosetting resin in the thermosetting resin portion is preferably 50 wt% or more, more preferably 70 wt% or more, further preferably 90 wt% or more, preferably 99.9 wt% or less, more preferably 99.7 wt% or less, further preferably 99.6 wt% or less, based on 100 wt% of the thermosetting resin portion. When the content of the thermosetting resin is not less than the lower limit and not more than the upper limit, the adhesiveness can be further improved, and dripping during 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% (total amount) based on 100 wt% of the total of all resin components contained in the thermosetting resin portion. When the content of the thermosetting resin is not less than the lower limit, the adhesiveness can be further improved, and dripping during heating can be further effectively suppressed.

The content of the thermosetting resin in the adhesive particle is preferably 2% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, particularly preferably 25% by weight or more, preferably 99.5% by weight or less, more preferably 99% by weight or less, still more preferably 98% by weight or less, based on 100% by weight of the adhesive particle. When the content of the thermosetting resin is not less than the lower limit and not more than the upper limit, the adhesiveness can be further improved, and dripping during heating can be further effectively suppressed.

In the adhesive particle having no base particle, the content of the thermosetting resin is preferably 70 wt% or more, more preferably 75 wt% or more, further preferably 80 wt% or more, preferably 99.5 wt% or less, more preferably 99 wt% or less, further preferably 98 wt% or less, based on 100 wt% of the adhesive particle. When the content of the thermosetting resin is not less than the lower limit and not more than the upper limit, the adhesiveness can be further improved, and dripping during heating can be further effectively suppressed.

In the adhesive particle having the base particles, the content of the 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 70% by weight or less, further preferably 60% by weight or less, further preferably 50% by weight or less, based on 100% by weight of the adhesive particle. When the content of the thermosetting resin is not less than the lower limit and not more than the upper limit, the adhesiveness can be further improved, and dripping during heating can be further effectively suppressed.

(inorganic oxide particles)

Examples of the inorganic oxide particles include silica, titania (titanium oxide), zinc oxide, alumina, glass, talc, kaolin, bentonite, and zirconium.

From the viewpoint of more effectively suppressing aggregation and more effectively suppressing dripping upon heating, the inorganic oxide particles preferably contain silica or titania, more preferably contain silica. The inorganic oxide particles are preferably silica or titania, more preferably silica, from the viewpoint of further improving the adhesiveness and improving the strength of the adhesive particles.

Examples of the silica include natural silica and synthetic silica. Examples of synthetic silica include hydrophilic silica and hydrophobic silica. From the viewpoint of stable quality, the silica is preferably synthetic silica, more preferably synthetic silica produced by a gas phase method.

The content of the inorganic oxide particles in the adhesive particle is preferably 0.25 wt% or more, more preferably 0.5 wt% or more, further preferably 1 wt% or more, particularly preferably 1.9 wt% or more, preferably 20 wt% or less, more preferably 15 wt% or less, further preferably 10 wt% or less, based on 100 wt% of the adhesive particle. When the content of the inorganic oxide particles is not less than the lower limit and not more than the upper limit, the adhesion can be further improved, and aggregation can be further effectively suppressed.

The content of the inorganic oxide particles is preferably 0.3 parts by weight or more, more preferably 0.6 parts by weight or more, still more preferably 1 part by weight or more, particularly preferably 2.5 parts by weight or more, and most preferably 2.9 parts by weight or more, based on 100 parts by weight of the thermosetting resin. The content of the inorganic oxide particles is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, still more preferably 10 parts by weight or less, and particularly preferably 7.6 parts by weight or less, based on 100 parts by weight of the thermosetting resin. When the content of the inorganic oxide particles is not less than the lower limit and not more than the upper limit, the adhesion can be further improved, and aggregation can be further effectively suppressed.

In the adhesive particle having no base particle, the content of the inorganic oxide particles is preferably 0.4 wt% or more, more preferably 0.9 wt% or more, further preferably 1.9 wt% or more, preferably 19.5 wt% or less, more preferably 14.5 wt% or less, further preferably 9.5 wt% or less, based on 100 wt% of the adhesive particle. When the content of the inorganic oxide particles is not less than the lower limit and not more than the upper limit, the adhesion can be further improved, and aggregation can be further effectively suppressed.

In the adhesive particle having no base particle, the content of the inorganic oxide particle is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, further preferably 2 parts by weight or more, and particularly preferably 2.5 parts by weight or more, based on 100 parts by weight of the thermosetting resin. In the adhesive particle having no base particle, the content of the inorganic oxide particles is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less, based on 100 parts by weight of the thermosetting resin. When the content of the inorganic oxide particles is not less than the lower limit and not more than the upper limit, the adhesion can be further improved, and aggregation can be further effectively suppressed.

In the adhesive particle having the base particle, the content of the inorganic oxide particles is preferably 0.25 wt% or more, more preferably 0.5 wt% or more, still more preferably 1.0 wt% or more, and particularly preferably 1.9 wt% or more, based on 100 wt% of the adhesive particle. In the adhesive particle having the base particle, the content of the inorganic oxide particles is preferably 12% by weight or less, more preferably 10% by weight or less, and still more preferably 6% by weight or less, based on 100% by weight of the adhesive particle. When the content of the inorganic oxide particles is not less than the lower limit and not more than the upper limit, the adhesion can be further improved, and aggregation can be further effectively suppressed.

In the adhesive particle having the base particles, the content of the inorganic oxide particles is preferably 0.3 parts by weight or more, more preferably 0.6 parts by weight or more, still more preferably 1.0 parts by weight or more, and particularly preferably 2.5 parts by weight or more, based on 100 parts by weight of the thermosetting resin. In the adhesive particle having the base particles, the content of the inorganic oxide particles is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 7.0 parts by weight or less, based on 100 parts by weight of the thermosetting resin. When the content of the inorganic oxide particles is not less than the lower limit and not more than the upper limit, the adhesion can be further improved, and aggregation can be further effectively suppressed.

(substrate particles)

The adhesive particles may or may not have base particles in the adhesive particles. The adhesive particle having the base particle inside is, for example, a coated particle in which a part of the surface of the base particle is coated with a coating layer or a plurality of particles, such as the adhesive particle 11 or the adhesive particle 21. The adhesive particle having no base particle inside refers to, for example, an adhesive particle having no coating portion as in the adhesive particle 1.

The base particles preferably contain a thermoplastic resin, from the viewpoint of suppressing peeling of the coating layer or the coating particles from the surface of the base particles, further improving adhesion, and controlling gaps with high accuracy.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, and polyisobutylene, acrylic resins such as polymethyl methacrylate and polymethyl acrylate, polyvinyl acetal resins, polyester resins, ethylene-vinyl acetate copolymer resins, ethylene-acrylic acid copolymer resins, polyurethane resins, and polyvinyl alcohol resins. The thermoplastic resin may be used in an amount of 1 or 2 or more.

The base particles preferably contain a pigment or dye from the viewpoints of enhancing blackness and suppressing occurrence of light leakage. The pigment or dye may be used in an amount of 1 or 2 or more. Light leakage is a phenomenon in which light from a backlight passes through a molten resin portion when a liquid crystal display element is turned on. Due to light leakage, the contrast of the liquid crystal display element may be reduced, or a display quality called white spot may be reduced.

Examples of the pigment include carbon black, titanium black, aniline black, iron oxide, lamp black, graphite, copper-chromium composite oxide, and copper-chromium-zinc composite oxide. The pigment preferably contains carbon black from the viewpoints of improving the blackness and suppressing occurrence of light leakage.

Examples of the dye include pyrazole azo dyes, anilino azo dyes, triphenylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxacyclopentene dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, pyrrole methylene dyes, triarylmethane dyes, azomethine dyes, perylene dyes, pyrene dyes, quaterrylene dyes, and quinophthalone dyes. The dye may be an acid dye, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azo dye, a disperse dye, an oil-soluble dye, a food dye, a dye in which 2 or more of their derivatives are mixed to be black, or the like.

From the viewpoint of improving the strength of the base material particles and suppressing occurrence of light leakage, the total content of the pigment and the dye in 100 wt% of the base material particles is preferably 1 wt% or more, more preferably 3 wt% or more, further preferably 5 wt% or more, preferably 20 wt% or less, more preferably 15 wt% or less, further preferably 10 wt% or less.

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

The CV value (coefficient of variation) of the particle diameter of the base material particles can be measured as follows.

CV value (%) = (ρ/Dn) ×100

ρ: standard deviation of particle diameter of the base material particles

Dn: average value of particle diameter of the base material particles

When the substrate is coated with a dispenser or the like, the 10% K value of the base material particles is preferably 10000N/mm from the viewpoint of preventing breakage of the substrate due to collision with the substrate and further improving adhesion ² Hereinafter, more preferably 7000N/mm ² The following is given. The lower limit of the 10% k value of the base particles is not particularly limited. The substrate particles may have a 10% K value of 10N/mm ² The above.

The 10% K value of the substrate particles can be determined as follows.

The base material particles were compressed by a micro compression tester under a condition of applying a maximum test load of 20mN for 60 seconds at 25℃on a smooth indenter end face of a cylinder (diameter: 50 μm, made of diamond). The load value (N) and the compression displacement (mm) at this time were measured. The 10% K value can be obtained from the obtained measurement value by the following formula. For example, "FISCHE RSCOPE H-100" manufactured by FISCHER Co., ltd.) is used as the micro-compression tester.

10% K value (N/mm) ² )＝(3/2 ^1/2 )·F·S ^-3/2 ·R ^-1/2

F: load value (N) at 10% compression deformation of base material particles

S: compression displacement (mm) of base material particles at 10% compression deformation

R: radius (mm) of substrate particle

From the viewpoint of practical use, the particle diameter of the base material 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, more preferably 29 μm or less, further preferably 24.5 μm or less.

The particle diameter of the base material particles is a diameter when the base material particles are in a spherical shape, and is a diameter when the base material particles are in a shape other than a spherical shape, assuming that the base material particles are in a spherical shape corresponding to the volume thereof.

The particle diameter of the base material particles is an average particle diameter obtained by measuring the base material particles by a particle diameter measuring device. Examples of the particle diameter measuring device include: a particle size distribution measuring machine using the principles of laser scattering, resistance value change, image analysis after photographing, and the like. Specifically, examples of the method for measuring the particle diameter of the base material particles include: a method of measuring about 100000 particle diameters by using a particle size distribution measuring apparatus (Multisizer 4, manufactured by BE CKMAN COULTER Co.), and measuring the average particle diameter. The average particle diameter represents a number average particle diameter.

In the adhesive particle having the base particle, the content of the base particle is preferably 13% by weight or more, more preferably 37% by weight or more, further preferably 63% by weight or more, preferably 99% by weight or less, more preferably 94% by weight or less, further preferably 87% by weight or less, based on 100% by weight of the adhesive particle. When the content of the base material particles is not less than the lower limit and not more than the upper limit, the adhesion can be further improved, and aggregation can be further effectively suppressed.

In the adhesive particle having the base particle, the content of the base particle is preferably 5% by volume or more, more preferably 10% by volume or more, further preferably 15% by volume or more, preferably 95% by volume or less, more preferably 85% by volume or less, further preferably 75% by volume or less, in 100% by volume of the adhesive particle. When the content of the base material particles is not less than the lower limit and not more than the upper limit, the adhesion can be further improved, and aggregation can be further effectively suppressed.

< adhesive >

The adhesive of the present invention comprises the adhesive particles and a binder. The adhesive particles are preferably dispersed in an adhesive and used as an adhesive. The adhesive is suitable for use in a light modulating layer and a light modulating laminate. The binder may be used in an amount of 1 or 2 or more.

The binder is not particularly limited. As the binder, an insulating resin is generally used. Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. The binder resin may be used in an amount of 1 or 2 or more.

Examples of the vinyl resin include: vinyl acetate resin, acrylic resin, styrene resin, and the like. Examples of the thermoplastic resin include: polyolefin resins, ethylene-vinyl acetate copolymers, polyamide resins, and the like. Examples of the curable resin include: epoxy resins, polyurethane resins, polyimide resins, unsaturated polyester resins, and the like. The curable resin may be a room temperature curable resin, a thermosetting resin, a photo curable resin, or a moisture curable resin. The curable resin may be used in combination with a curing agent. Examples of the thermoplastic block copolymer include: styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrides of styrene-butadiene-styrene block copolymers and hydrides of styrene-isoprene-styrene block copolymers. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

The adhesive and the binder preferably contain a thermoplastic component or a thermosetting component. The adhesive and the binder may contain a thermoplastic component or a thermosetting component.

The adhesive may contain various additives such as a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, and a flame retardant, in addition to the adhesive particles and the adhesive.

The content of the binder in the adhesive is preferably 10 wt% or more, more preferably 30 wt% or more, further preferably 50 wt% or more, particularly preferably 70 wt% or more, preferably 99.99 wt% or less, and more preferably 99.9 wt% or less, based on 100 wt% of the adhesive. If the content of the binder is not less than the lower limit and not more than the upper limit, the adhesion can be further improved.

The content of the adhesive particles in the adhesive is preferably 0.01 wt% or more, more preferably 0.1 wt% or more, still more preferably 80 wt% or less, still more preferably 60 wt% or less, still more preferably 40 wt% or less, particularly preferably 20 wt% or less, and most preferably 10 wt% or less, based on 100 wt% of the adhesive. When the content of the adhesive particles is not less than the lower limit and not more than the upper limit, the adhesion can be further improved and the gap can be controlled with high accuracy.

< light modulation laminate >)

The light control laminate of the present invention includes a 1 st substrate, a 2 nd substrate, and a light control layer disposed between the 1 st substrate and the 2 nd substrate. In the light control laminate of the present invention, the material of the light control layer contains the adhesive particles.

The PDLC type dimming laminate 51 includes a 1 st substrate 52, a 2 nd substrate 53, and a dimming layer 54. The light modulation layer 54 is disposed between the 1 st substrate 52 and the 2 nd substrate 53. A sealant may be disposed around the light modulation layer 54 between the 1 st substrate 52 and the 2 nd substrate 53.

The light control layer 54 includes a liquid crystal capsule 54A, an adhesive 54B, and a plurality of adhesive particles 1. The liquid crystal capsules 54A are dispersed in the adhesive 54B. The liquid crystal capsules 54A are held in a capsule shape in the adhesive 54B. The liquid crystal material may be dispersed in the binder in the form of capsules, or may be dispersed in the binder in the form of a continuous phase.

The adhesive particles 1 are spherical adhesive particles. In the PDLC type light control laminate 51, the thermosetting resin portion of the adhesive particle 1 is thermally cured.

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

The SPD dimming laminate 61 includes a 1 st substrate 62, a 2 nd substrate 63, and a dimming layer 64. The dimming layer 64 is disposed between the 1 st substrate 62 and the 2 nd substrate 63. A sealant may be disposed around the light modulation layer 64 between the 1 st substrate 62 and the 2 nd substrate 63.

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

The dimming layer 64 includes droplets 64A of a dimming suspension and a resin matrix 64B. Droplets 64A of the dimming suspension are dispersed in a resin matrix 64B. The droplets 64A of the dimming suspension are held in the resin matrix 64B in a droplet state.

The droplet 64A of the dimming suspension includes a dispersion medium 64Aa and dimming particles 64Ab. The light control particles 64Ab are dispersed in the dispersion medium 64 Aa.

Transparent electrodes may be formed on the surface of the 1 st substrate and the surface of the 2 nd substrate. As a material of the transparent electrode, indium Tin Oxide (ITO) or the like is given.

The dimming layer has dimming properties. The light-adjusting property is a property in which the visible light transmittance changes according to the presence or absence of application of an electric field, and the amount of incident light can be adjusted. Examples of the mechanism of action for changing the visible light transmittance include: PDLC (Polymer Dispersed Liquid Crystal), SPD (Suspended Particle Device), guest-host liquid crystal using liquid crystal, TN (Twisted Nematic), VA (Vertical Al ignment), IPS (In-Plane-Switching), and the like. The material of the light adjusting layer is not particularly limited, and may be any material as long as it has light adjusting properties.

The dimming laminate is preferably a PDLC dimming laminate or an SPD dimming laminate.

PDLC mode

The dimming layer preferably further comprises a binder and a liquid crystal material dispersed in the binder.

The liquid crystal material is not particularly limited. The liquid crystal material preferably has a property of changing an orientation by applying an electric field. The liquid crystal material may be dispersed in the binder in the form of a continuous phase, or may be dispersed in the binder in the form of liquid crystal droplets or liquid crystal capsules. Examples of the liquid crystal material include nematic liquid crystal and cholesteric liquid crystal.

Examples of the nematic liquid crystal material include cyanobiphenyl, phenyl esters, azobenzene oxides, fluorobiphenyl, carbonates, and schiff bases. The nematic liquid crystal may be used in an amount of 1 or 2 or more.

As a material of the cholesteric liquid crystal, there can be mentioned: steroid cholesterol derivatives, schiff bases, azo compounds, benzoate compounds, biphenyl compounds, terphenyl compounds, cyclohexyl carboxylic acid esters, phenylcyclohexane compounds, biphenylcyclohexane compounds, pyrimidine compounds, dioxane compounds, cyclohexyl cyclohexane compounds, cyclohexyl ethane compounds, cyclohexane compounds, diphenylacetylene compounds, alkenyl compounds, stilbene compounds, nematic liquid crystals such as condensed polycyclic compounds, smectic liquid crystals, and materials obtained by adding chiral components of optically active materials such as schiff bases, azo compounds, esters and biphenyls to the mixed liquid crystals thereof. The cholesteric liquid crystal material may be used in an amount of 1 or 2 or more.

The adhesive holds the liquid crystal material and inhibits the flow of the liquid crystal material. The binder is not particularly limited. The adhesive is preferably insoluble in a liquid crystal material, has an intensity capable of withstanding an external force, and has high transmittance for reflected light and incident light. As a material of the binder, there may be mentioned: water-soluble polymer materials such as gelatin, polyvinyl alcohol, cellulose derivatives, polyacrylic polymers, ethyleneimine, polyethylene oxide, polyacrylamide, polystyrene sulfonate, polyamidine, and isoprenoid sulfonic acid polymers, and materials capable of aqueous emulsification such as fluorine resins, silicone resins, acrylic resins, polyurethane resins, and epoxy resins. The binder may be used in an amount of 1 or 2 or more.

The binder is preferably crosslinked by a crosslinking agent. The crosslinking agent is not particularly limited. The crosslinking agent preferably forms a crosslink between the binders and can harden, insolubilize, or insolubilize the binders. Examples of the crosslinking agent include acetaldehyde, glutaraldehyde, glyoxal, potassium alum hydrate of a polyvalent metal salt compound, adipic acid dihydrazide, melamine formaldehyde oligomer, ethylene glycol diglycidyl ether, polyamide epichlorohydrin, and polycarbodiimide. The crosslinking agent may be used alone or in combination of 1 or more than 2.

SPD mode

The dimming layer preferably further comprises a resin matrix and a dimming suspension dispersed in the resin matrix.

The dimming suspension includes a dispersion medium and dimming particles dispersed in the dispersion medium.

As the light control particles, there may be mentioned: and carbon-based materials such as polyiodide and carbon black, metal materials such as copper, nickel, iron, cobalt, chromium, titanium, and aluminum, and inorganic compound materials such as silicon nitride, titanium nitride, and aluminum oxide. Further, particles obtained by coating these materials with a polymer may be used. The light control particles may be used in an amount of 1 or 2 or more.

The dispersion medium disperses the light control particles in a flowable state. The dispersion medium is preferably the following material: the material is a material which is selectively attached to the light control particles, coats the light control particles, and acts to move the light control particles to a droplet phase separated from the phase when the light control particles are separated from the phase of the resin matrix, and has no conductivity and no affinity with the resin matrix. The dispersion medium is preferably a liquid copolymer having a refractive index similar to that of the resin matrix when the light control laminate is produced. As the liquid copolymer, a (meth) acrylate oligomer having a fluoro group or a hydroxyl group is preferable, and a (meth) acrylate oligomer having a fluoro group and a hydroxyl group is more preferable. When such a copolymer is used, the monomer units of the fluoro group or the hydroxy group are oriented toward the light-adjusting particles, and the remaining monomer units stabilize the droplets of the light-adjusting suspension in the resin matrix. Therefore, the light control particles are easily dispersed in the light control suspension, and when the light control particles are separated from the phase of the resin matrix, the light control particles are easily induced into the liquid droplets having separated phases.

Examples of the (meth) acrylate oligomer having a fluoro group or a hydroxyl group include: 2, 2-trifluoroethyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, 3, 5-trimethylhexyl acrylate/2-hydroxypropyl acrylate/fumaric acid copolymer, butyl acrylate/2-hydroxyethyl acrylate copolymer, 2, 3-tetrafluoropropyl acrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, 1H, 5H-octafluoropentyl acrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer 1H, 2H-heptadecafluorodecyl acrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, 2-trifluoroethyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer 2, 3-tetrafluoropropyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer 1H, 5H-octafluoropentyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, 1H, 2H-heptadecafluorodecyl methacrylate/butyl acrylate/2-hydroxyethyl acrylate copolymer, and the like. Further, these (meth) acrylate oligomers more preferably have both a fluoro group and a hydroxyl group.

The weight average molecular weight of the (meth) acrylate oligomer is preferably 1000 or more, more preferably 2000 or more, preferably 20000 or less, more preferably 10000 or less.

The dimming layer may be prepared using a resin material for forming the resin matrix and the dimming suspension.

The resin material is preferably a resin material cured by irradiation of energy rays. The resin material cured by irradiation with energy rays includes a polymer composition containing a photopolymerization initiator and a polymer compound cured by energy rays such as ultraviolet rays, visible rays, and electron beams. The polymer composition includes a polymerizable monomer having an ethylenically unsaturated group and a photopolymerization initiator. Examples of the polymerizable monomer having an ethylenically unsaturated group include a non-crosslinkable monomer and a crosslinkable monomer.

Examples of the non-crosslinkable monomer include: styrene monomers such as styrene, α -methylstyrene, chlorostyrene and the like as vinyl compounds; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; vinyl acetate compounds such as vinyl acetate, vinyl butyrate, vinyl laurate and vinyl stearate; halogen-containing monomers such as vinyl chloride and vinyl fluoride; alkyl (meth) acrylate compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate; oxygen atom-containing (meth) acrylate compounds such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meth) acrylate; nitrile-containing monomers such as (meth) acrylonitrile; halogen-containing (meth) acrylate compounds such as trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate; olefin compounds such as diisobutylene, isobutylene, linear olefin, ethylene, and propylene, which are α -olefin compounds; isoprene, butadiene, and the like as conjugated diene compounds.

Examples of the crosslinkable monomer include: vinyl monomers such as divinylbenzene, 1, 4-divinyloxybutane, and divinylsulfone as vinyl compounds; polyfunctional (meth) acrylate compounds such as tetramethylolmethane tetra (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 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, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, and 1, 9-nonanediol di (meth) acrylate; triallyl (iso) cyanurate, triallyl trimellitate, diallyl phthalate, diallyl acrylamide, diallyl ether as allyl compounds; alkoxy silane compounds such as tetramethoxy silane, tetraethoxy silane, methyltrimethoxy silane, methyltriethoxy silane, ethyltrimethoxy silane, ethyltriethoxy silane, isopropyltrimethoxy silane, isobutyltrimethoxy silane, cyclohexyltrimethoxy silane, n-hexyltrimethoxy silane, n-octyltriethoxy silane, n-decyltrimethoxy silane, phenyltrimethoxy silane, dimethyldimethoxy silane, dimethyldiethoxy silane, diisopropyldimethoxy silane, trimethoxysilyl styrene, γ - (meth) acryloxypropyl trimethoxy silane, 1, 3-divinyl tetramethyl disiloxane, methylphenyl dimethoxy silane, diphenyl dimethoxy silane, and the like; alkoxysilanes containing a polymerizable double bond such as vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, dimethoxyethylvinylsilane, diethoxymethylvinylsilane, diethoxyethylvinylsilane, ethylmethyldivinylbenzene, methylvinyldimethoxysilane, ethylvinyldimethoxysilane, methylvinyldiethoxysilane, ethylvinyldiethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-acryloxypropyl trimethoxysilane; cyclic siloxanes such as decamethyl cyclopentasiloxane; modified (reactive) silicone oils such as single-terminal modified silicone oils, both-terminal silicone oils, and side chain type silicone oils; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride.

The photopolymerization initiator may be: 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-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and (1-hydroxycyclohexyl) phenyl ketone, and the like.

The resin material may contain an organic solvent-soluble resin, a thermoplastic resin, poly (meth) acrylic acid, and the like. The resin material may contain various additives such as a coloring inhibitor, an antioxidant, and an adhesion-imparting agent, and may also contain a solvent.

SPD mode

(1 st and 2 nd substrates)

The 1 st substrate and the 2 nd substrate are preferably substrates having light transmittance (light-transmissive substrates). The 1 st substrate and the 2 nd substrate are preferably transparent substrates. For example, light is transmitted from one side of the transparent substrate to the other side via the transparent substrate. For example, when a substance located on one side of the transparent substrate is visually observed through the transparent substrate, the substance can be visually observed and confirmed. Transparent also includes translucent. The transparent substrate may be colorless and transparent, or may be colored and transparent.

The material of the 1 st substrate and the 2 nd substrate is not particularly limited. The material of the 1 st substrate may be the same as or different from the material of the 2 nd substrate. Examples of the material of the substrate include glass and a resin film. Examples of the glass include soda lime glass, lead glass, borosilicate glass, and glass having various compositions for general construction and other uses, and functional glass such as heat reflecting glass, heat absorbing glass, and reinforced glass. Examples of the resin film include polyester films such as polyethylene terephthalate, polyolefin films such as polypropylene, and resin films such as acrylic resin films. The transparent substrate is preferably a resin substrate, more preferably a resin film, and even more preferably a polyethylene terephthalate film, from the viewpoint of excellent transparency, formability, adhesiveness, workability, and the like.

The 1 st substrate and the 2 nd substrate preferably include a substrate main body and a transparent conductive film formed on a surface of the substrate main body so that an electric field for dimming can be applied. Examples of the transparent conductive film include Indium Tin Oxide (ITO) and SnO ₂ In ₂ O ₃ Etc.

From the viewpoint of improving the visibility of the light control laminate, the visible light transmittance of the 1 st and 2 nd substrates is preferably 75% or more, more preferably 80% or more.

The visible light transmittance of the substrate may be measured by spectrometry or the like, and the measurement is performed in accordance with ISO 13837:2008. Further, the measurement may be performed by a method in accordance with JIS K6714 standard or the like.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited to the following examples.

The following materials were prepared.

Thermosetting resin:

thermosetting resin A (bisphenol A type epoxy resin, "EXA-850-CRP" manufactured by DIC Co., ltd.)

Thermosetting resin B (bisphenol A type epoxy resin, "EXA-4850-150" manufactured by DIC Co., ltd.)

Thermosetting resin C (1, 12-dodecanediol diglycidyl ether, "DO D-DEP" manufactured by Synthesis Co., ltd.)

Curing agent:

amine curing agent (2, 5 (2, 6) -bis (aminomethyl) bicyclo [2.2.1] heptane)

Inorganic oxide particles:

silica dispersion (TOL-ST, manufactured by Nissan chemical Co., ltd., "toluene dispersion having an average particle diameter of 12nm, 40% by weight of silica particles)

Titanium dioxide powder (SUPER-TITANIA F-6A, manufactured by Zhaowa electric company, "average particle size 15 nm)

Substrate particles:

substrate particle D (MICROPEARL SP-209, manufactured by Water chemical industry Co., ltd., "average particle size 9.0 μm, CV value 5%)

Base particle E (MICROPEARL KBN-509, manufactured by water chemical industry Co., ltd., "average particle diameter 9.0 μm, CV value 4%)

Example 1

(1) Preparation of adhesive particles

In a separable flask, 47 parts by weight of a thermosetting resin A, 47 parts by weight of a thermosetting resin B, 6 parts by weight of a thermosetting resin C, 50 parts by weight of polyvinylpyrrolidone (Fuji photo-seal sheet and Wako pure chemical industries, ltd. "K-30"), 16.6 parts by weight of cetylammonium bromide and 1670 parts by weight of methanol were mixed and dissolved, and then 6.6 parts by weight of an amine curing agent was added. After reacting at 45℃for 10 hours, the silica dispersion was added so that the silica particles became 2.9 parts by weight, and the reaction was further carried out at 45℃for 10 hours. Then, the mother liquor was separated, washed with methanol, and dried under vacuum at 25 ℃ for 24 hours to obtain adhesive particles in which inorganic oxide particles were dispersed in the particle main bodies (thermosetting resin portions).

(2) Preparation of PDLC-based dimming laminate

As a material for the 1 st and 2 nd substrates, a PET film having a thickness of 50 μm was prepared. An acrylic hard coat resin (LIODURAS TYZ, manufactured by TOYOBO INJECTS) in which zirconia particles were dispersed was coated on one surface of a PET film, and then the film was cured by UV irradiation to form a first hard coat layer having a thickness of 0.8. Mu.m. An acrylic hard coat resin (LIOD URAS TYAB, manufactured by Toyo ink Co., ltd.) was coated on the other surface of the PET film, and then cured by UV irradiation to form a second hard coat layer having a thickness of 2.0. Mu.m. Thus, a base film was obtained.

The substrate film was set in a vacuum apparatus, and vacuum evacuation was performed. Vacuum degree reaches 9.0X10 ^-4 After Pa, argon gas was introduced, and SiO was formed on the surface of the first hard coat layer in this order from the first hard coat layer side by DC magnetron sputtering under an argon gas atmosphere _x Layer, siO ₂ Layer and SiO _x A layer on which an indium tin oxide (ito) layer is laminated. Specifically, snO is used ₂ An ITO sintered body target of 7 wt% was set to a chamber pressure of 3.5X10 using a cathode having a maximum horizontal magnetic flux density of 1000 Gauss on the target surface ^-1 Pa, ar gas and O ₂ The ratio of gases was set to 100:1, and a conductive layer (indium tin oxide layer) having a thickness of 18nm was formed by introducing a vacuum apparatus. Then, annealing treatment was performed at 160℃for 9 minutes using an IR heating oven (manufactured by MINO GROUP Co.) to obtain the 1 st substrate and the 2 nd substrate (substrates of transparent conductive films). 15 pieces/cm on the surface of the 1 st substrate ² And dispersing the adhesive particles. Subsequently, a light control material (prepared by the method described in "Ma cromolecules," volume 26, pages 6132 to 6134 (1993)) was laminated on the 2 nd substrate. At this time, at 2kgf/cm ² The mixture was heated at 120℃for 100 minutes to bond the adhesive particles to the 1 st and 2 nd substrates, thereby preparing a light control laminate.

Examples 2 to 5 and comparative example 1

Adhesive particles and light control laminates 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 base material particles D, 75 parts by weight of thermosetting resin A, 25 parts by weight of thermosetting resin B, 312.5 parts by weight of polyvinylpyrrolidone (Fuji photo-seal sheet and photo-pure chemical Co., ltd. "K-30"), 62.5 parts by weight of cetyltrimethylammonium bromide and 12500 parts by weight of methanol were mixed and dissolved, and then 12.5 parts by weight of an amine curing agent was added. After reacting at 45℃for 10 hours, the silica dispersion was added so that the silica particles became 7.1 parts by weight, followed by reacting at 45℃for 10 hours. Then, the mother liquor was separated, washed with methanol, and dried under vacuum at 25 ℃ for 24 hours to obtain adhesive particles in which the surfaces of the base particles were covered with a thermosetting resin portion and inorganic oxide particles were dispersed in the covered portion (thermosetting resin portion). A light control laminate was produced in the same manner as in example 1, except that the obtained adhesive particles were used.

Example 7

An adhesive particle and a light control laminate were produced in the same manner as in example 6, except that the base particle D was changed to the base particle E.

Comparative example 2

Into a separable flask, 10 parts by weight of base 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 in which 10 parts by weight of styrene monomer, 0.1 part by weight of silica dispersion and ammonium peroxodisulfate were dissolved in 30 parts by weight of ion-exchanged water was added, and silica particles were made 1 part by weight and reacted at 70℃for 10 hours. Then, after mother liquor separation and washing with ion-exchanged water, drying was performed under reduced pressure at 55 ℃ for 24 hours, thereby producing particles having no thermosetting resin portion and the surfaces of the base particles were coated with a thermoplastic resin. A dimming laminate was prepared in the same manner as in example 1, except that the obtained particles were used.

(evaluation)

(1) Cohesiveness (Single particle ratio)

The cross section of the adhesive particle was cut out from the obtained light control laminate using an ion milling device (HITACHI HIGH-IM 4000 manufactured by techenologies corporation) so as to pass through the vicinity of the center of the adhesive particle. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification was set at 800 times, 10 fields of view were randomly selected, and adhesive particles were observed. The ratio (%) of the number of unagglomerated adhesive particles to the number of total adhesive particles was defined as the single particle fraction. The higher the single particle ratio, the lower the aggregation of particles.

(2) Ejectability of

The obtained adhesive particles and epoxy resin (jER 828, manufactured by MITSUBISHI CHEMICAL Co.) were filled into a syringe, and deaerated to obtain an adhesive. The blocking of the adhesive particles at the time of 5cm discharge of the adhesive obtained under the conditions of a drawing speed of 50 mm/min, a discharge pressure of 0.2MPa and a nozzle diameter of 0.25mm was visually confirmed by using a dispenser (SHOTMASTER 300, manufactured by MUSASHI-ENG INEERING). The ejection property was determined according to the following criteria.

[ criterion for determining the ejectability ]

O: can spray 5cm without blockage

O: can spray out 3cm to less than 5cm without blocking

X: blocking occurs at a distance of less than 3cm

(3) Resistance to breakage by ejection

The adhesive particles after the above-mentioned discharge property test were observed for breakage by using a digital microscope (VHX-2000, manufactured by KEYENCE Co.). The image magnification was set to 200 times, and any 500 adhesive particles were observed. The resistance to breakage due to ejection of the adhesive particles was determined according to the following criteria.

[ criterion for judging resistance to breakage due to ejection ]

O: less than 5 broken adhesive particles

O: the number of broken adhesive particles is 5 or more and less than 20

X: broken adhesive particles of 20 or more

(4) Drop inhibitory effect

The transparent conductive film was prepared as the 1 st substrate and the 2 nd substrate. 15 pieces/cm on the surface of the 1 st substrate ² The obtained adhesive particles are dispersed. Next, the 2 nd substrate is laminated. Then, the mixture was heated at 180℃for 40 minutes, and observed with a digital microscope (VHX-2000, manufactured by KEYENCE Co., ltd.)Whether the surface of the particles is dripped or not. The image magnification was set to 200 times, and any 50 adhesive particles were observed. Drip inhibition was determined according to the following criteria.

[ criterion for drip inhibition ]

O: the adhesive particle of the dripping liquid is less than 5

O: the number of adhesive particles in the dripping liquid is more than 5 and less than 15

Delta: the number of adhesive particles of the dripping liquid is more than 15 and less than 30

X: the number of adhesive particles in the dripping liquid is more than 30

(5) Adhesiveness (tensile yield stress)

Using the obtained adhesive particles, a test body (test sample) was prepared according to the adhesive test a. The tensile yield stress of the test piece at 23℃was measured using a TENSILON Universal materials tester (manufactured by A & D company, "RTI-1310") (adhesion test A). The adhesiveness was determined according to the following criteria.

[ criterion for adhesive Property ]

O: the tensile yield stress is above 0.12MPa

O: a tensile yield stress of 0.07MPa or more and less than 0.12MPa

X: tensile yield stress of less than 0.07MPa

The composition and results of the adhesive particles are shown in tables 1 and 2 below.

TABLE 1

TABLE 2

Symbol description

1 … adhesive particle

2 … particle body (thermosetting resin part)

3 … inorganic oxide particles

11 … adhesive particle

12 … coating (coating)

13 … inorganic oxide particles

14 … substrate particles

21 … adhesive particle

22 … coating (multiple particles)

23 … inorganic oxide particles

24 … substrate particles

51 … PDLC dimming laminate

52 … first substrate 1

53 … No. 2 substrate

54 … dimming layer

54A … liquid crystal capsule

54B … adhesive

61 … SPD dimming laminate

62 … 1 st substrate

63 … substrate 2

64 … dimming layer

Droplets of 64A … dimming suspension

64Aa … dispersion medium

64Ab … dimming particles

64B … resin matrix

Claims

1. An adhesive particle comprising:

a thermosetting resin part, and a plurality of inorganic oxide particles,

the inorganic oxide particles are dispersed in the thermosetting resin portion, or the inorganic oxide particles are adhered to the surface of the thermosetting resin portion.

2. The adhesive particle according to claim 1, wherein,

the inorganic oxide particles are silica.

3. The adhesive particle according to claim 1 or 2, wherein,

the thermosetting resin of the thermosetting resin part is an epoxy resin.

4. The adhesive particle according to any one of claim 1 to 3, wherein,

the adhesive particles have base material particles inside,

the substrate particles comprise a thermoplastic resin.

5. The adhesive particle according to claim 4, wherein,

the substrate particles comprise a pigment or dye.

6. An adhesive, comprising:

the adhesive particle according to any one of claims 1 to 5, and

and (3) an adhesive.

7. A light control laminate is provided with: a 1 st substrate, a 2 nd substrate, and a light modulation layer disposed between the 1 st substrate and the 2 nd substrate,

the material of the light control layer contains the adhesive particle according to any one of claims 1 to 5.