JPH07241932A - Anti-fogging agent coated synthetic resin article and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide scratch resistance, weathering resistance and anti-fogging properties for a long time by forming a heat-generating pattern layer using an electrically conductive paste with a specified resin and the electrically conductive paste contg. a binder resin consisting of a mixture of specified resins, an electrical conductivity providing agent and a solvent. CONSTITUTION:A synthetic resin article with an anti-fogging coating is formed of a base sheet made of a synthetic resin, a heat-generating pattern layer using an electrically conductive paste formed on a film or a molding and a silicone hard coat layer formed on the pattern layer. In addition, the heat-generating pattern layer using the electrically conductive paste is formed of a binder resin consisting of a satd. polyester resin, a mixture of a satd. polyester resin and a vinyl chloride resin, a mixture of a satd. polyester resin and a vinyl chloride- vinyl acetate copolymer resin or a mixture of a satd. polyester resin, a vinyl chloride resin and a vinyl chloride-vinyl acetate copolymer resin and an electrically conductive paste contg. an electrical conductivity providing agent and a solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifogging coated synthetic resin article, and particularly to an antifogging property which can be used for a heat-generating pattern layer and a window material for vehicles having a hard coat layer formed on the pattern layer. The present invention relates to a coated synthetic resin article and a method for manufacturing the same.

[0002]

2. Description of the Related Art In order to reduce the weight of vehicles, it has been attempted to use synthetic resins as window materials in place of inorganic glass. Originally, in an atmosphere where the temperature and humidity are different on the outside and inside of the vehicle, there is a problem that moisture in the atmosphere causes dew condensation on the surface of the window for the vehicle to fog up the window and hinder the visibility. The same problem occurs when a synthetic resin is used instead. Further, in producing a synthetic resin window, it is indispensable to apply a hard coat to the surface of the window in order to improve scratch resistance and weather resistance. Conventionally, the following method has been adopted as a technique for imparting anti-fogging property to a synthetic resin window material. (1) A surfactant is added to a synthetic resin window material and molding is performed using the resin. (2) The surface of the synthetic resin window material is coated with a hydrophilic polymer or the one in which a surfactant is added. (3) A film containing a surfactant is attached to the surface of the synthetic resin window material.

However, the synthetic resin window material obtained by each of the above-mentioned methods can sufficiently exhibit the antifogging performance at the initial stage of its production, but if it is used for a long period of time, the antifogging property remarkably deteriorates. There is a problem that it ends up. Further, the surface of the synthetic resin window material is easily scratched and the weather resistance is insufficient, so that the long-term durability may be poor. More specifically,
The window material obtained by the above method (1) has a limited antifogging property because the surfactant is not concentrated in the surface layer, and thus imparts excellent antifogging property. Is difficult,
Further, since the synthetic resin material itself forms the surface layer, it may not be able to withstand long-term use due to poor scratch resistance and weather resistance of the surface.

Further, the window material obtained by the method (2) has poor scratch resistance because the hydrophilic polymer absorbs water and becomes soft, and the hydrophilic polymer absorbs and releases water. There is also a problem in weather resistance due to repeated aging, and further, the surfactant may be released by long-term use and the antifogging property may be deteriorated. The window material obtained by the above method (3) has a problem in long-term use because the synthetic resin film itself forms a surface layer and thus has poor scratch resistance and weather resistance. The best way to solve such problems is to apply a conductive paste on the surface of the synthetic resin window material and cure it, and adjust the resistance value so that the amount of heat required to exhibit the anti-fog function can be secured. (Specifically, it is performed by adjusting the thickness, width, length, number of heating wires, etc.), and then baked on the entire surface of the synthetic resin window material coated with the conductor paste. This is a method of forming a hard coat film.

[0005]

However, in the method of forming the hard coat film on the entire surface of the resin window material coated with the above-mentioned conductor paste as a pattern of the heating wire, the adhesiveness to the synthetic resin article is good. And also has heat resistance and weather resistance, and a conductor paste that can realize a low resistance value that can secure a heat generation amount necessary for exhibiting an antifogging function, a synthetic resin article, and the conductor paste. With a hard coat agent that can maintain good adhesion and weather resistance without eroding the paste part even when contacting with a hard coat liquid for improving the abrasion resistance of the No combination has been obtained, and a method of forming a hard coat film on the entire surface of the resin window material coated with a conductor paste as a pattern of heating lines has not been put into practical use. The object of the present invention is to produce a synthetic resin article having antifogging performance, not only exhibiting the antifogging performance for a long period of time, but also a synthetic resin which originally has both scratch resistance and weather resistance to be provided. Providing an article.
Another object of the present invention is to produce a synthetic resin article having an antifogging property without problems such as elution of the conductor paste and peeling of the conductor paste from the synthetic resin article when the hard coat is applied.

[0006]

The above object of the present invention can be achieved by the following constitutions. That is, an anti-fogging coating composition comprising a heat-generating pattern layer using a conductive paste formed on a synthetic resin substrate, film or molded product, and a silicone-based hard coat layer formed on the pattern layer. In the resin article, the heat generating pattern layer using the conductor paste is (1) saturated polyester resin, (2)
A mixture of saturated polyester resin and vinyl chloride resin,
(3) A binder resin, a conductivity-imparting agent, and a solvent made of a mixture of a saturated polyester resin and a vinyl chloride-vinyl acetate copolymer resin or (4) a mixture of a saturated polyester resin, a vinyl chloride resin, and a vinyl chloride-vinyl acetate copolymer resin. It is an antifogging coated synthetic resin article formed from a conductor paste containing a. A colored shielding portion is provided in the peripheral portion of the heat-generating pattern layer of the antifogging coated synthetic resin article of the present invention, or the heat-generating pattern layer is provided in a plurality of rows of heating lines and both ends of the plurality of rows of heating lines. It can be configured to include a pair of electrode portions.

The above object of the present invention can also be achieved by the following configuration. That is, (1) saturated polyester resin on a substrate, film or molded article made of synthetic resin,
(2) Saturated polyester resin and vinyl chloride resin mixture, (3) Saturated polyester resin and vinyl chloride-vinyl acetate copolymer resin mixture, or (4) Saturated polyester resin, vinyl chloride resin and vinyl chloride-vinyl acetate copolymer resin. A conductive paste containing a mixture of a binder resin, a conductivity-imparting agent and a solvent is applied and cured to form an exothermic pattern layer, and a silicone hard coat layer is applied on the pattern layer to prevent curing. A method for producing a cloudy coated synthetic resin article. The silicone-based hard coat layer of the synthetic resin article of the present invention has the following formula RSi (OH) ₃ where R is an alkyl group having 1 to 3 carbon atoms, a vinyl group, 3,3,3-tri Fluoropropyl group,
It is selected from the group consisting of γ-aminopropyl group, γ-methacryloxypropyl group and γ-glycidoxypropyl group. It is preferable to use a colloidal silica-containing organopolysiloxane composed of a partial condensate of (1) and colloidal silica or another colloidal metal oxide in water or an alcohol dispersion.

The antifogging coating component and the like will be described in detail below. 1. Structure of Conductor Paste that Exhibits Antifogging Function Resin as Binder As the binder resin, acrylic resin, epoxy resin, phenol resin, polyester resin, etc. may be used, but polyester resin is most preferable. The reason is that a paste having the lowest resistance value can be obtained because silver powder and copper powder can be easily dispersed, it has excellent adhesion to polycarbonate resin, acrylic resin, etc., it has good heat resistance, and it has good Has weather resistance.
This is because it has excellent solvent resistance. Examples of the polyester resin used as the binder resin of the present invention include aromatic carboxylic acids (eg, phthalic acid,
It consists of dibasic acid, which is a mixture of trimellitic acid, etc.) and aliphatic carboxylic acid (eg, maleic acid, succinic acid, etc.) to give flexibility, and glycols (eg, polyethylene glycol, polypropylene glycol, etc.) A saturated polyester resin is preferable, and its molecular weight is 5,000 to 40,000, more preferably 10,000.
It is 0 to 30,000. Solvent resistance when the molecular weight is too low, heat resistance is reduced, silver powder if the molecular weight is too high,
It is difficult to disperse copper powder etc. and the resistance value becomes high.

As the binder resin, it is possible to use a polyester resin alone, a saturated polyester resin, a saturated polyester resin and a vinyl chloride resin, and / or a mixture of vinyl chloride and a vinyl acetate copolymer resin. The content of the vinyl chloride resin mixed with the saturated polyester resin or the copolymer resin of vinyl chloride and vinyl acetate is preferably 0 to 40% by weight in the saturated polyester resin. When the saturated polyester resin alone is used as the binder resin, an isocyanate compound or a blocked isocyanate compound may be further contained as a crosslinking agent. The content of this cross-linking agent in the saturated polyester resin is preferably 0 to 20% by weight. (Since the saturated polyester resin is an addition reaction of dibasic acid and glycols and some OH groups remain, This OH group reacts with the isocyanate compound).
Also, for high boiling ether-based and alcohol-based solvents used during hard coating or primer coating,
Especially when it is necessary to improve solvent resistance, it is preferable to use a vinyl chloride resin or a mixture with a vinyl chloride / vinyl acetate copolymer resin, or to incorporate an isocyanate or a blocked isocyanate as a crosslinking agent.

Conductivity imparting agent Conductive metal powder such as silver powder is used. The metal powder is preferably surface-treated (effective as a lubricant) with a long-chain organic acid such as stearic acid to improve dispersibility. The conductivity-imparting agent preferably has a flake shape, and in the case of a flake shape, a fine size having a diameter of 1 to 30 μm and a thickness of 3 to 5 μm is preferable. In addition to silver powder, conductive metal powder such as copper or zinc powder can be used. Solvents are not particularly limited as long as they have high solubility and do not adversely affect printability, but butyl cellosolve acetate and ethyl cellosolve acetate, which are high boiling solvents, are preferably used. The solid content of the conductor paste is preferably + and is in the range of 35 to 75% by weight. It is more preferably 50 to 70% by weight. This is because if the solid content of the conductor paste is low, a low resistance value cannot be exhibited, and if the solid content is high, the dispersibility of conductive metal powder such as silver powder is impaired.

2. Optimum conditions for the thickness of the conductive paste and the curing conditions In order to develop the antifogging function on the surface of the synthetic resin article, 20
A calorific value of about 0 to 800 W / m ² is required. Therefore, for example, in the window frame made of synthetic resin shown in FIG.
A desired amount of heat generation can be obtained by changing the resistance value between the electrode portions 1a and 1b, in other words, the thickness, width, length, and number of the heating wires 2 formed from the conductor paste. However, the film thickness of the electrode portions 1a, 1b and the heating wire 2 is preferably about 5 to 30 μm. More preferably 10-2
It is 0 μm. When the film thickness of the electrode portions 1a, 1b and the heating wire 2 is 5 μm or less, the required resistance value cannot be obtained,
When the thickness is more than μm, the flexibility of the coating film of the conductor pattern forming the heating wire 2 is lowered, cracks are likely to occur, and liquid sagging is likely to occur from the boundary portion during hard coating. The conductor paste is cured at about 80 to 130 ° C. in order to eliminate the residual solvent as much as possible. However, the temperature of the temperature range is set such that it is dried for a relatively long time and the high temperature region is dried for a shorter time. The curing time is preferably about 20 minutes to 3 hours. If the drying is insufficient, the binder resin may be eluted or a sufficiently low resistance value may not be obtained.

3. Silicone type hard coat material Although not particularly limited, typical silicone type hard coat agents as shown below can be preferably used. RSi (OH) ₃ (wherein R is an alkyl group having 1 to 3 carbon atoms, a vinyl group, a 3,3,3-trifluoropropyl group,
It is selected from the group consisting of γ-aminopropyl group, γ-methacryloxypropyl group and γ-glycidoxypropyl group. Preferred R is a methyl group or a γ-glycidoxypropyl group. The colloidal silica-containing organopolysiloxane coating agent comprising the partial condensate of 1) and a water or alcohol dispersion of colloidal silica or another colloidal metal oxide is used. When the resin material is polycarbonate, heat-resistant acrylic resin or the like, it is particularly preferable to provide an undercoat layer having good adhesiveness on both the above-mentioned silicone-based hard coat agent and the synthetic resin material. An acrylic solvent type undercoat layer containing a cross-linking agent and an ultraviolet absorber, if necessary, in a resin or a copolymer with another monomer copolymerizable with an acrylic monomer is preferably used.

When the synthetic resin article is a window,
In order to hide the terminals or conductors connected to the electrode portions 1a, 1b from the outside of the window and improve the design, masking printing may be performed on the peripheral portion of the synthetic resin window with a shielding ink. Such masking printing is usually performed before applying the conductor paste. The heat-generating pattern layer using the conductor paste of the present invention and the silicone-based hard coat layer formed on the pattern layer can be used as a synthetic resin article in a synthetic resin plate, a synthetic resin film, or a synthetic resin molded article. it can. For example, it can be used as a window material for vehicles, a window of a cold storage, a daylighting window in a cold region, and the like. Further, when the synthetic resin article of the present invention is a vehicle window material or the like, the durability of the synthetic resin article is improved by providing it not only on the front surface but also on the back surface.

[0014]

EFFECT OF THE INVENTION According to the present invention, the amount of heat generated is required to impart the anti-fog function to the synthetic resin plate, resin film, or resin molded product made of a synthetic resin such as polycarbonate resin or acrylic resin by direct screen printing. Apply a pattern made of conductive paste whose resistance value is adjusted so that
Since this can be baked and a hard coating can be applied from the top of the conductor pattern layer without any problem, it is possible to impart anti-fogging property to the surface of the synthetic resin article and also the conductor paste portion. In addition, it has become possible to improve scratch resistance and weather resistance of the entire surface of the synthetic resin article. Further, this saturated polyester resin-based conductive pattern layer has good adhesion to the surface of the synthetic resin article and also has weather resistance, does not elute when contacted with the silicone-based hard coat liquid, and is corroded. Nothing. Furthermore, by selecting a conductor paste that can secure the amount of heat required to provide an anti-fog function and combining it with a silicone hard coat that has good adhesion, scratch resistance, and weather resistance, Scratching,
A coated synthetic resin article having good weather resistance can be obtained. Also, as with the inorganic glass, it is possible to apply a hard coating on the printed conductor paste without any problems, so it is possible to prevent the heat generation line part and other parts that are printed with the conductor paste pattern. It has become possible to finish the surface of a synthetic resin article having cloudiness with an excellent appearance.

[0015]

EXAMPLES Examples of the present invention will be described below. Example 1 (Preparation of undercoat paint) While maintaining 320 g of propylene glycol monomethyl ether in a nitrogen atmosphere at 90 ° C., 90 g of methyl methacrylate, 10 g of γ-methacryloxypropyltrimethoxysilane, and 0.8 g of azobisisobutyronitrile were used. The mixture was added over 2 hours and kept at the same temperature for 5 hours. Then, ethyl cellosolve 760
g, 5% of a 10% aqueous solution of di-n-butylamine, 1.1 g of diethylene glycol, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole 20 g
Was added to give an undercoat paint A. (Preparation of top coat) 135 g of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex O-40, water dispersion type, solid content 40%) and colloidal antimony oxide (manufactured by Nissan Chemical Industry Co., Ltd., trade name) Antimony oxide sol 1510P, water dispersion type, solid content 12%)
To 110 g, 207 g of methyltrimethoxysilane and 7.0 g of acetic acid are added, and the mixture is stirred for 3 hours while maintaining the temperature at 50 ° C. for hydrolysis. Then, n-butanol 195
g, 195 g of ylpropyl alcohol, 1.26 g of sodium acetate and 11.0 g of acetic acid were added to obtain a top coating composition A.

(Molding of automobile window material) Conductor paste A (manufactured by Fujikura Kasei Co., Ltd., product name DOTITE FA-323) on the surface of a polycarbonate plate (manufactured by Tsutsunaka Plastic Industry Co., Ltd., product name POLYCAACE) which has been washed in advance. , A binder resin is a saturated polyester resin and a cross-linking agent is a block isocyanate, a specific resistance of 3.5 × 10 ⁻⁵ Ω
cm) is screen-printed, and a plurality of heating lines having a line width of 1.0 mm arranged in parallel with a line spacing of 15 mm and a pair of electrode portions having a width of 20 mm are applied to the left and right ends of these heating lines.
The conductor paste was cured by heating at 120 ° C. for 45 minutes to form a heating wire pattern layer. The polycarbonate plate with a heating wire was heated at 180 ° C. for 10 minutes, and was subjected to hot press bending to form an automobile window material A.

The undercoat paint A was applied to the automobile window material A with the heating wire by a dipping method (dip coating method) and dried by heating in a hot air drying oven at 120 ° C. for 30 minutes. At this time, the printed surface portion of the heating line portion was not corroded by the undercoat paint A, and a clean coated surface was obtained without elution components. Next, the above-mentioned top coating composition A was applied to the polycarbonate automobile window material A coated with the undercoat layer thus obtained by a dipping method, and the coating was carried out in a hot air drying oven.
It was heated and dried at 20 ° C. for 60 minutes to be cured. At this time as well, the printed surface portion of the heating line portion was not corroded, and the coated surface was clean without elution. The thus-obtained coated automotive window material A with a heating wire has a transparent and clean coated surface, and both the heating wire portion and the transparent portion have abrasion resistance A, adhesiveness 100/100, and water resistance. The results were good, and the appearance, hardness, and adhesiveness after 2000 hours of the sunshine weatherometer test were also good. Further, it was confirmed that the anti-fogging property was completely cleared within 10 minutes (6 to 7 minutes) after energization.

The coating film was evaluated by the following method. Abrasion resistance: Rubbing with # 0000 steel wool was performed to check the scratch resistance and judged as follows. A: No scratches even with strong rubbing. B: If you rub it hard, it will get a little scratched. C: Slight scratches cause scratches. Adhesiveness: In a so-called cross-cut tape test, 11 parallel lines were put on the coated surface with a knife at 1 mm intervals to form 11 parallel lines, cross-cut 100 squares, and then attach a cellophane adhesive tape on it. Peel off the tape 10
The number is shown by the number of squares that do not separate from the zero squares. Water resistance: After standing in warm water at 60 ° C. for 7 days, the presence or absence of abnormality such as whitening, cracking or peeling of the film is confirmed. Accelerated weather resistance test: Weather resistance was evaluated by a sunshine carbon arc weather ohmmeter. The black panel temperature was 63 ± 3 ° C., and the water spray was performed in a cycle of 12 minutes / hour. The weather resistance was also evaluated using a xenon arc weatherometer. The black panel temperature was 63 ± 3 ° C. Water spraying was performed for 18 minutes / 2 hours, and the irradiation intensity was 0.35 W / m ² at 340 nm. Next, the antifogging property was measured by the following method.
Each synthetic resin window material with each heating wire is attached to a passenger car, and it is placed in an environment where the temperature outside the vehicle is 0 ° C, the temperature inside the vehicle is 30 ° C, and the humidity inside is 80% RH.
A voltage of 2 V was applied, and the time until the cloudiness cleared was measured.

Example 2 (Preparation of top coat) 80 g of γ-glycidoxypropyltrimethoxysilane, 144 of methyltrimethoxysilane
g, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name Snowtex O, water dispersion type, solid content 20%) 71
g and 170 g of 0.1N hydrochloric acid aqueous solution are mixed, and the temperature is 80 ° C.
The mixture was stirred for 2 hours while maintaining the above temperature to carry out hydrolysis. To the ternary cohydrolyzate solution thus obtained, 146 g of ethyl cellosolve and 1.3 g of ammonium perchlorate were added to obtain a top coating composition B. Conductor paste B (manufactured by Fujikura Kasei Co., Ltd., DOTITE FA-) on the surface of an acrylic plate (manufactured by Sumitomo Chemical Co., Ltd., trade name Sumipex) that has been washed in advance.
517 (trade name), a type in which the binder resin is a mixture of saturated polyester resin and vinyl chloride / vinyl acetate copolymer resin, specific resistance of 3.0 × 10 ⁻⁵ Ωcm) is screen-printed, and the line spacing is 20 mm, and the lines are parallel to each other. Arranged line width 1.5
A plurality of mm heating wires and a pair of electrode parts having a width of 20 mm were applied to the left and right ends of these heating wires and heated at 90 ° C. for 2 hours to cure the conductor paste.

The acrylic plate with the heating wire was heated at 140 ° C. for 10
After heating for a minute, an automobile window material B was formed by a vacuum forming method.
The top coating material B is applied by flow coating (flow coating method) to the window material B for automobiles with a heating wire, and the coating material is applied in a hot air drying oven at 80
It was dried by heating for 3 hours. At this time, the printed surface portion of the heating wire portion did not change at all, and a clean coated surface was obtained without whitening due to elution. The automobile window material B with a heating wire thus obtained has a transparent and clean coated surface,
Abrasion resistance A and adhesion of 100 /
100, the water resistance was also good, and the appearance, hardness, and adhesion after 2000 hours of the sunshine weather o-meter test were also good. In addition, it was confirmed that the antifogging property was completely cleared within 10 minutes (5 to 6 minutes) after energization.

Example 3 and Comparative Examples 1 and 2 Preliminarily washed polycarbonate film (manufactured by Tsutsunaka Plastic Industry Co., Ltd., trade name Polycaace, 0.5 mm)
(A thickness) was screen-printed with an acrylic black masking ink and dried at 120 ° C. for 10 minutes to form a colored shielding portion having a width of 40 mm at the peripheral portion of the shape corresponding to the rear window. Further, the same heating line pattern as in Example 1 was screen-printed on the colored shield portion by using the same conductor paste A as in Example 1, and at 45 ° C. at 120 ° C.
The conductor paste was cured by heating for a minute. At this time,
A binder resin as shown in Table 1 was screen-printed on the colored shield with a conductive paste of a phenolic resin and an epoxy resin as shown in Table 1 by the same method, and heated at 120 ° C. for 45 minutes. Then, the conductor paste was cured.

[0022]

[Table 1]

Polycarbonate films with heating wires, which are made of different conductor pastes and have different colored shielding parts, are cut into window material shapes and attached to a mold for injection molding, and a heat-resistant acrylic resin (KAMAX T- manufactured by Rohm & Haas Co.) is used. 24
0) was injected and various window materials C were created by the so-called film insert molding method. The undercoat paint A prepared in Example 1 was applied to the various window materials C produced by the above-mentioned molding method by a dipping method, and heated and dried at 120 ° C. for 60 minutes in a hot air drying oven. The polycarbonate film insert heat-resistant acrylic window material C coated with the obtained undercoat layer was coated with the top coating composition A prepared in Example 1 by a dipping method and heated in a heating / drying furnace for 12 hours.
It was heated and dried at 0 ° C. for 60 minutes to be cured. Among the various types of coated heat-resistant acrylic window materials C with colored shields and heating wires thus obtained, the window material C using the conductor paste A is transparent and has a clean coated surface. Abrasion resistance A, adhesiveness 100/100, and water resistance are good for both parts and transparent parts, and xenon weatherometer test 20
The appearance, hardness, and adhesion after 00 hours were also good. Further, it was confirmed that the anti-fogging performance was completely cleared within 10 minutes (6 to 7 minutes) after energization. However, it was confirmed that the window material C using the other conductor paste peeled off the heating wire, and the anti-fogging performance did not completely clear the fog even after 20 minutes had passed after energization.

Examples 4 and Comparative Examples 3 and 4 (Preparation of undercoat paint) 400 g of propylene glycol monomethyl ether, 170 g of methyl methacrylate, 2
While maintaining a mixture of 30 g of hydroxyethyl methacrylate at 80 ° C. under a nitrogen atmosphere, a solution of 1.0 g of azobisisobutyronitrile in 200 g of propylene glycol monomethyl ether was added over 2 hours, and the temperature was kept at the same temperature for 5 hours. I kept it. Thereafter, 400 g of propylene glycol monomethyl ether, 2- (2'-hydroxy-5'-octylphenyl) benzotriazole 21
g to give an undercoat paint B. (Preparation of top coat) Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name Snowtex O-40, water dispersion type, solid content 40%) 150 g, colloidal antimony oxide (manufactured by Nissan Chemical Industry Co., Ltd., trade name) Sun colloid AMT-130S, alcohol dispersion type solid content 30
%), 220 g of methyltrimethoxysilane and 10 g of acetic acid were added, and the mixture was stirred for 2 hours while maintaining the temperature at 55 ° C. for hydrolysis. Then isopropyl alcohol 2
50 g, n-butanol 200 g, sodium acetate 1.
3 g and 11 g of acetic acid were added to obtain a top coating composition C.

(Window material with heating wire) A conductor paste C (manufactured by Fujikura Kasei Co., Ltd.) on the surface of a window material D injection-molded using a heat-resistant acrylic resin (Asahi Kasei Co., Ltd., trade name Delmore H350A) Product name DOTITE FA-333, binder resin is a saturated polyester resin alone type, specific resistance 3.0 × 10 ^-5 Ωcm) is screen-printed and the line spacing is 1
A plurality of heating wires with a width of 1.0 mm arranged in parallel at 5 mm and a pair of electrode parts with a width of 20 mm are applied to the left and right ends of these heating wires and heated at 120 ° C. for 60 minutes to cure the conductor paste. Let At this time, the conductor paste C was screen-printed on the window material D by the same method to form the same heating line pattern, and cured at each drying temperature and time of Comparative Examples 3 to 4. The undercoating paint C was applied to the window material D with a heating wire having different drying conditions by the dipping method and dried for 30 minutes, and then the overcoating paint C was applied by the dipping method and dried by heating at 110 ° C. for 60 minutes to be cured. . The window material D thus obtained is shown in Table 2.
As shown in the figure, if the drying temperature is too low or the drying time is too short, the conductor paste may elute and whiten, or the conductor paste may be corroded by the solvent of the coating liquid and float up. Occurred.

[0026]

[Table 2]

[0027]

According to the present invention, the resin article can exhibit the anti-fogging property by the heating pattern layer using the conductor paste.
Moreover, the silicon resin hard coat layer formed on the entire surface of the resin article can improve scratch resistance and weather resistance.

[Brief description of drawings]

FIG. 1 is a diagram illustrating a pattern of a heating wire and an electrode portion using a conductor paste formed on a synthetic resin article according to an embodiment of the present invention.

[Explanation of symbols]

 1 ... Electrode part, 2 ... Heating wire

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location // B29K 83:00 (72) Inventor Hiroyoshi Nanzato 8-1 Saiwaicho, Utsunomiya City, Tochigi Prefecture

Claims (5)

[Claims] 1. An anti-fog comprising a heat-generating pattern layer using a conductive paste formed on a synthetic resin substrate, film or molded product, and a silicone-based hard coat layer formed on the pattern layer. In the heat-resistant synthetic resin article, the exothermic pattern layer using the conductor paste is (1) saturated polyester resin, (2) mixture of saturated polyester resin and vinyl chloride resin, (3) saturated polyester resin and vinyl chloride-acetic acid. It is formed from a conductor paste containing a binder resin comprising a mixture of vinyl copolymer resin or (4) a mixture of saturated polyester resin, vinyl chloride resin and vinyl chloride-vinyl acetate copolymer resin, a conductivity-imparting agent and a solvent. An anti-fogging coated synthetic resin article characterized. 2. The anti-fogging coated synthetic resin article according to claim 1, wherein a colored shielding portion is provided in the peripheral portion of the heat-generating pattern layer. 3. The anti-fog coated synthetic resin according to claim 1, wherein the heat-generating pattern layer comprises a plurality of rows of heating wires and a pair of electrode portions provided at both ends of the plurality of rows of heating wires. Goods. 4. The silicone-based hard coat layer has the following formula RSi (OH) ₃ , wherein R is an alkyl group having 1 to 3 carbon atoms, a vinyl group, a 3,3,3-trifluoropropyl group,
It is selected from the group consisting of γ-aminopropyl group, γ-methacryloxypropyl group and γ-glycidoxypropyl group. 4. A colloidal silica-containing organopolysiloxane comprising a partial condensate of 1) and a water or alcohol dispersion of colloidal silica or another colloidal metal oxide. Anti-fog coated synthetic resin article. 5. A (1) saturated polyester resin, (2) a mixture of a saturated polyester resin and a vinyl chloride resin, and (3) a saturated polyester resin and a vinyl chloride-vinyl acetate copolymer on a substrate, film or molded article made of a synthetic resin. A mixture of polymerized resins or (4) a binder resin consisting of a mixture of saturated polyester resin, vinyl chloride resin, and vinyl chloride-vinyl acetate copolymer resin, a conductor paste containing a conductivity-imparting agent and a solvent is applied and cured to generate heat. A patterned pattern layer is formed, a silicone-based hard coat layer is applied onto the patterned layer, and the layer is cured, and a method for producing an antifog-coated synthetic resin article.