JPS63157131A - Light adjustable composite acrylic body - Google Patents

Abstract

PURPOSE:To provide a light adjustable composite body which is light in weight, soft and resistant to breakage by using a transparent acrylic resin which is improved in the adhesiveness to transparent conductive films as substrate. CONSTITUTION:The transparent conductive films 2 provided to the substrates 1 consisting of the transparent acrylic resin disposed to confront each other and an electrochromism material which makes a phase change in a solid state is previously interposed therebetween. The resin which satisfies the equation and is improved in the adhesiveness to the films 2 is used for the above- mentioned acrylic resin. In the formula, F denotes the number of moles (mumol/ cm<2>) at which a basic dye can react with or stick to the acrylic resin per unit area of the acrylic resin surface and Hv denotes the Vickers hardness in accordance with JIS Z-2244. The above-mentioned resin is obtd. by using, for example, methyl methacrylate, as an essential component and copolymerizing the same with monoalcohol, diol or triol and ester of (meth)acrylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a dimming acrylic resin composite having an electrochromic effect.

<Conventional technology> Conventionally, a transparent electrode, a coloring layer, an insulating layer, etc. are stacked on a glass substrate, and then an aluminum electrode is placed on top of the glass substrate, and when a voltage is applied to both electrodes, the coloring layer causes an oxidation-reduction reaction and changes color.
Many light control glass material combinations utilizing the so-called electrochromism effect have been proposed.

This light control glass composite has excellent adhesion between the glass substrate and the transparent electrode film, such as indium oxide-tin oxide, tin oxide, antimony oxide, etc. I can withstand it quite well. Furthermore, glass substrates have many advantages such as excellent weather resistance, and currently, those using glass substrates are the mainstream.

However, glass substrates have drawbacks such as being extremely brittle and easily damaged, being heavy, lacking in flexibility, difficult to process such as cutting, and difficult to increase in size.

<Problems to be solved by the invention> In order to solve the above problems, it is conceivable to use an acrylic resin substrate, which has the best transparency and weather resistance, as a new substrate. There is an essential problem in that it is not possible to form a thin film of tin oxide-based or tin oxide-antimony oxide-based substances on the surface of an acrylic resin substrate.

In view of this situation, the present invention aims to provide a dimming acrylic resin composite with excellent performance by making it possible to form a transparent conductive thin film by using a specific acrylic resin.

In other words, the gist of the present invention is to apply a transparent conductive thin film based on indium oxide-tin oxide or tin oxide and antimony oxide on the surface of a transparent acrylic resin that satisfies the following formula (1). A photochromic acrylic resin composite F×HV≧0.4, in which acrylic resin substrates having a transparent conductive effect made of ...(1) [wherein F is the number of moles (μmol/cm
”), and HV represents Vickers hardness measured by a method based on JIS Z-2244.

The present invention will be described below with reference to drawings of embodiments.

FIG. 1 shows a cross-sectional view of an embodiment of the light-tuning acrylic resin composite of the present invention, in which 1: substrate, 2: transparent conductive thin film, 3: reducing coloring layer, 4: oxidizing coloring layer. , 5; dielectric layer; 6; conductive transfer; 7; insulating layer; 8; electrode extraction portion.

Among these, the acrylic resin specified by the above formula is used for the substrate 1, but in order to improve the adhesion of the transparent conductive film 2, the value of FXHV is required to be 0.4 or more.

This numerical value is a value that controls the presence of functional groups in the substrate 1 and a predetermined hardness, but if it is less than 0.4, sufficient adhesion cannot be obtained.

The reason for this is not clear, but when a certain level of functional groups that react with the basic dye on the surface of the substrate 1 are present, they coordinate with the atomic groups forming the transparent conductive thin film 2, and this coordination effect increases the adhesion. Further, if the surface hardness of the substrate 10 is above a certain level,
This is thought to be due to the enhanced anchoring effect between the transparent conductive thin film 2 and the substrate 1.

Acrylic resins that satisfy the above formula include methyl methacrylate as a main component, monoalcohols such as propatool and butanol, diols such as ethylene glycol and 1,3-propanediol, and triols such as trimethylolethane and trimethylolpropane. Examples include, but are not limited to, acrylic resins obtained by copolymerizing esters of other polyols and acrylic acid and/or methacrylic acid.

In the present invention, the above acrylic resin is used as a substrate and a transparent conductive thin film is formed on the surface thereof. As a method for this, ion blasting, RF or DC sputtering, etc. can be used.

In this case, the transparent conductive material is indium oxide, which is unaffected by electrochromic materials.
Tin oxide type or tin oxide antimony oxide type is preferred.

Moreover, the thickness of the transparent conductive thin film 2 is 400 to 3000.
Laminated at about A. When the thickness is set to this level, a surface electrical resistance value of about 102 to 10[Omega]/mouth can be obtained, and the electrode can function satisfactorily as the electrode of the present invention.

Next, an electrochromic material that changes phase in a solid state is interposed.

Substances that have an electrochromic effect include organic and inorganic materials, and each has a different coloring mechanism, but the common point is that they utilize changes in the absorption spectrum of molecules or colored species produced by electrochemical reactions. are doing. Then, a composite is formed by combining the electrochromic material and the ionic conductor, which are its constituent elements.

Among these, ion conductors are sometimes used in solution or solid form. In the case of a solution, an electrolyte solution in which lithium perchlorate is dissolved in a nonaqueous solvent such as sulfuric acid, an inorganic aqueous solution, or propylene carbonate or r-butyl lactone is used. This ionic conductor cannot be used because it deteriorates the acrylic resin referred to in the present invention. Therefore, the structure of the present invention needs to be a solid composite that undergoes a phase change.

In the present invention, the substance 3 that is colored by a reduction reaction having an electrochromic effect includes WOI, Tie
, , Inorganic substances such as MoO2, V, Og, Nb, 01, and the substance 4 that is colored by oxidation reaction include IrO
x.

Examples include inorganic substances such as Rh20B, NlOx, Cr, and 03.

Other organic substances may also be used, but they are not limited to this example.

The ion conductive layer 5 is made of, for example, Ta205, Cr, O,
Dielectric films such as β-alumina, No, Zrt, S
1! Examples include ultrasonic ion conductors such as POt, but are not limited to this example.

A thin film of these substances is formed on an acrylic resin substrate 1 having a transparent conductive thin film as used in the present invention. The thin film is formed on the substrate by a vacuum evaporation method or a combination with a printing method, but the thickness of these films may be adjusted to suit the purpose of use and is not regulated by the present invention. .

After forming each thin film layer as described above, the acrylic resin substrate 1 having a transparent conductive thin film is used as a counter electrode, and the transfer electrode 6 is bonded with a conductive paste in advance, and then set with an insulating material 7. Seal. The insulating agent in this case is an organic adhesive that is adhesive to ordinary acrylic resin.

Then, a conductive wire is taken out from the terminal electrode 8, and the dimming acrylic resin composite according to the present invention is completed.

<Example> Examples of the present invention will be described below, and evaluation was performed using the following method.

(The value of IIF (the number of moles that a basic dye can react or adhere to per unit area of the substrate surface) is 0, and the concentration of Eisen methyl violet is 10 P/l using IN sodium acetate buffer (pH 4, 5). A solution of 50 x 50 mm was immersed in this solution for 48 hours, washed with water-99% methanol solution-water, and after wiping off the water, the absorbance of light at 580 nm was measured. .

In part, a calibration curve of dye concentration was obtained separately from the Eisen methyl violet solution, and the number of moles of functional groups that could react with or attach to the basic dye was calculated.

(2) Hma (Vickers hardness) Compliant with JIS Z-2244 (3) Adhesion Commercially available cellophane tape was adhered to the surface of the transparent conductive thin film, and the tape was peeled off rapidly upward to examine the situation.

Evaluation: O: All (no peeling) ×: Peeling off even in small amounts (4) Surface electrical resistance value Measurements were made using the usual four-probe measurement method.

Example 1 0.05 parts by weight of benzoyl peroxide was added as a polymerization initiator to a mixture of 20 parts by weight of 1.6-hexanediol diacrylate and 80 parts by weight of methyl methacrylate, and 60 parts by weight of benzoyl peroxide was added as a polymerization initiator.
Polymerization was carried out at .degree. C. to produce a transparent acrylic resin substrate with a thickness of 2 fi.

Sputtering was performed on this substrate using a high frequency magnetron sputtering device at a temperature of 60°C in an argon atmosphere containing 3% oxygen (3 mtn torr) using indium oxide/tin oxide (9515 parts by weight) as a target. , an indium oxide-tin oxide thin film having a thickness of 800 A was formed. Various thin films were sequentially laminated on this substrate as shown in FIG.

Using a vacuum evaporation method using an electron beam, iridium oxide was deposited on the above substrate as a substance 4 that colored by an oxidation reaction.
OA, tantalum oxide 5000A as ion conductive material 5
, tungsten oxide 50 as substance 3 for reduction reaction
00X was vacuum deposited and laminated. Next, a conductive silver paste was adhered to the transfer 6, and the transparent conductive acrylic resin substrate 1 was placed thereon as a counter electrode, and sealed with an epoxy resin. Then, a lead wire was connected from the terminal electrode.

Table 1 shows the adhesive performance of the acrylic resin and transparent conductive thin film of this example, and the properties of the obtained light control acrylic resin composite.

Example 2 To a mixture of 33 parts by weight of ethylene glycol diacrylate and 67 parts by weight of methyl methacrylate, parts by weight of benzoyl peroxide O,OS were added as a polymerization initiator, and a 2-thick transparent mixture was prepared in the same manner as in Example 1. An acrylic resin substrate was produced.

Next, in the same manner as in Example 1, a conductive thin film was formed using tin oxide/antimony oxide (97.5/2.5 parts by weight) to form a light control acrylic resin composite.

The obtained performance is shown in Table 1.

Example 3 0.05 parts by weight of benzoyl peroxide was added as a polymerization initiator to a mixture of 30 parts by weight of ethylene glycol diacrylate and 180 parts by weight of methyl methacrylate.
A transparent acrylic resin substrate with a thickness of 0.5 mm was prepared in the same manner as described above.

Next, a conductive thin film was formed in the same manner as in Example 1 to obtain an indium oxide-tin oxide transparent conductive acrylic resin substrate.

Vacuum depositing 3000A of tungsten oxide onto the substrate,
Using acrylamide methylpropane sulfonic acid as a proton electrolyte, layers were sequentially laminated by printing method and vacuum evaporation method, conductive transfer was performed in the same manner as in Example 1, counter electrode was attached, and lead wires were taken out. A resin composite was obtained.

The performance of the composite is shown in Table 1.

The composite of this example had flexibility against external forces, which could not be obtained with conventional glass substrates.

Comparative Example 1 A transparent conductive thin film was formed in the same manner as in Example 1 using a commercially available polymethyl methacrylate plate (Acrylite L, manufactured by Mitsubishi Rayon Co., Ltd., thickness 2 txx), but the adhesion was poor and A photochromic acrylic resin composite referred to in the invention could not be obtained.

This performance is shown in Table 1.

As is clear from Table 1 above, the light control acrylic resin board assembly of the present invention fully exhibits the light control function and has excellent characteristics.

<Effects of the Invention> Since the present invention has the configuration as detailed above, it has various properties as a dimming composite, such as being lightweight, having flexibility that cannot be achieved with glass, and being unbreakable. , it can be applied to various applications that could not be used in the past, such as vehicles with strong vibrations and construction, and its effects are extremely large.

[Brief explanation of the drawing]

FIG. 1 shows a schematic cross-sectional view of an embodiment of the invention. 1... Acrylic resin substrate 2... Transparent conductive thin film 3... Reducing coloring layer 4... Oxidizing coloring layer 5... Ion conductive layer 6... Conductive transfer 7... Insulation Layer 8...Electrode extraction partial procedure amendment December 24, 1986 Commissioner of the Patent Office Black 1) Akio Yu! 2 Kake F1
, Indication of the case Patent application filed on December 22, 1986 (1) 2, Title of the invention ・″ ・′ ・ −・”Dimmer acrylic resin composite 3, Relationship with the person making the amendment Patent Applicant: 2-3-19 Kyobashi, Chuo-ku, Tokyo (603) Mitsubishi Rayon Co., Ltd. President Akio Kawasaki 5, Date of amendment order Voluntary amendment 6, Subject of amendment

Claims (1)

[Claims] An acrylic resin substrate having a transparent conductive effect, comprising a transparent conductive thin film of indium oxide to tin oxide or tin oxide to antimony oxide on a transparent acrylic resin surface that satisfies the following formula (1). A dimming acrylic resin composite comprising two substrates facing each other and a solid phase-changeable electrochromic material interposed between the substrates. F×H_V≧0.4...(1) [Wherein, F is the number of moles (μmol) with which the basic dye can react or adhere per unit area of the surface of the transparent acrylic resin.
/cm^2), and H_V represents the Bitkers hardness measured by a method based on JIS Z-2244]