JP3844255B2 - Anti-fogging coated synthetic resin window material for vehicles - Google Patents

Description

【００２３】
該着色遮蔽部付き、互いに異なる導電体ペーストからなる発熱線付きポリカーボネートフィルムを窓材形状に切断して射出成形用金型に貼り付け、耐熱アクリル樹脂（ローム＆ハース社製ＫＡＭＡＸ Ｔ−２４０）を射出し、いわゆるフィルムインサート成形法にて各種窓材Ｃを作成した。
上記成形法により作製された各種窓材Ｃに実施例１で調整した下塗り塗料Ａを浸漬法で塗布して熱風乾燥炉で１２０℃、６０分間加熱乾燥した。
得られた下塗り層で被覆されたポリカーボネートフィルムインサート耐熱アクリル窓材Ｃに実施例１で調整した上塗り塗料Ａを浸漬法にて塗布し加熱乾燥炉で１２０℃、６０分間加熱乾燥し硬化させた。
このようにして得られた着色遮蔽部付き、発熱線付き被覆耐熱アクリル各種窓材Ｃのうち導電体ペーストＡを用いた窓材Ｃは透明で、清浄なコート面を有しており、発熱線部分、透明部分共に耐摩耗性Ａ、付着性１００／１００、耐水性も良好で、さらにキセノンウェザーオメーターテスト２０００時間後の外観、硬度、付着性も良好であった。また、防曇性能は通電後１０分以内（６〜７分後）に完全に曇りが晴れることを確認できた。しかしながら、他の導電体ペーストを用いた窓材Ｃは発熱線の剥離を起こしたり、また防曇性能は通電後２０分を経過しても完全に曇りが晴れないことが確認された。
【００２４】
実施例４および比較例３、４
（下塗り塗料の調整）
プロピレングリコールモノメチルエーテル４００ｇ、メタアクリル酸メチル１７０ｇ、２−ヒドロキシエチルメタクリレート３０ｇの混合物を窒素雰囲気下で８０℃に保ちながら、アゾビスイソブチロニトリル１．０ｇをプロピレングリコールモノメチルエーテル２００ｇに溶かした溶液を２時間かけて加え、さらに５時間同温度に保った。その後プロピレングリコールモノメチルエーテル４００ｇ、２−（２’−ヒドロキシ−５’−オクチルフェニル）ベンゾトリアゾール２１ｇを加え下塗り塗料Ｂとした。
（上塗り塗料の調整）
コロイダルシリカ（日産化学工業（株）製、商品名スノーテックスＯ−４０、水分散タイプ、固形分４０％）１５０ｇ、コロイダルアンチモンオキサイド（日産化学工業（株）製、商品名サンコロイドＡＭＴ−１３０Ｓ、アルコール分散タイプ固形分３０％）３５ｇにメチルトリメトキシシラン２２０ｇ、酢酸１０ｇを加えて温度を５５℃に保ちながら２時間撹拌して加水分解を行った。その後イソプロピルアルコール２５０ｇ、ｎ−ブタノール２００ｇ、酢酸ナトリウム１．３ｇ、酢酸１１ｇを添加して上塗り塗料Ｃとした。
【００２５】
（発熱線付き窓材）
耐熱アクリル樹脂（旭化成（株）製、商品名デルモアＨ３５０Ａ）を用いて射出成形された窓材Ｄの表面に導電体ペーストＣ（藤倉化成（株）製、商品名ドータイトＦＡ−３３３、バインダー樹脂が飽和ポリエステル樹脂単独のタイプ、比抵抗３．０×１０^-5Ωｃｍ）をスクリーン印刷して線間隔１５ｍｍで平行に配した線幅１．０ｍｍの複数の発熱線およびこれらの発熱線の左右両端に幅２０ｍｍの一対の電極部を塗着し、１２０℃で６０分間加熱して導電体ペーストを硬化させた。
このとき窓材Ｄに同様の方法で導電体ペーストＣをスクリーン印刷し、同様の発熱線パターンを作成し、比較例３〜４の各乾燥温度と時間で硬化させた。
該乾燥条件の異なる発熱線付き窓材Ｄに下塗り塗料Ｃを浸漬法にて塗布して３０分間乾燥後、上塗り塗料Ｃを浸漬法により塗布し、１１０℃で６０分間加熱乾燥して硬化させた。
このようにして得られた窓材Ｄは表２の通り、乾燥温度が低すぎたり乾燥時間が短かすぎるなど乾燥不十分の場合、導電体ペーストが溶出して白化したり、導電体ペーストがコート液の溶剤に侵食され浮きあがるなどの不良を発生した。
【００２６】
【表２】

【００２７】
【発明の効果】
本発明によれば、導電体ペーストを用いる発熱パターン層により合成樹脂車両用窓材は防曇性が発揮でき、しかも合成樹脂車両用窓材全体の表面に形成されたシリコン樹脂製のハードコート層により耐擦傷性、耐侯性の向上を達成することができる。
【図面の簡単な説明】
【図１】 本発明の一実施例の合成樹脂物品上に形成される導電体ペーストを用いた発熱線と電極部のパターンを説明する図である。
【符号の説明】
１…電極部、２…発熱線[0001]
[Industrial application fields]
TECHNICAL FIELD The present invention relates to an antifogging coated synthetic resin article, and in particular, an antifogging coated synthetic resin that can be used for an exothermic pattern layer and a vehicle window material having a hard coat layer formed on the pattern layer.Vehicle window materialAnd its manufacturing method.
[0002]
[Prior art]
In order to reduce the weight of the vehicle, it has been attempted to use a synthetic resin instead of inorganic glass as the window material. Originally, in an atmosphere where the temperature and humidity on the outside and inside of the vehicle are different, moisture in the atmosphere condenses on the surface of the window for the vehicle and fogs the window, obstructing the field of view. The same problem occurs when a synthetic resin is used. Further, in producing a synthetic resin window, it is indispensable to carry out a hard coat on the window surface in order to improve the scratch resistance and weather resistance. Conventionally, the following methods have been adopted as techniques for imparting antifogging properties to synthetic resin window materials.
(1) A surfactant is added to a synthetic resin window material and molded using the resin.
(2) The surface of the synthetic resin window material is coated with a hydrophilic polymer or a surfactant added thereto.
(3) A film containing a surfactant is attached to the surface of the synthetic resin window material.
[0003]
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 used for a long time, the antifogging property is remarkably lowered. There is a problem. Further, the surface of the synthetic resin window material is easily damaged, and the durability is inferior due to insufficient weather resistance.
More specifically, the window material obtained by the method (1) has an excellent antifogging property because the surfactant is not concentrated in the surface layer, and is excellent. Since it is difficult to impart antifogging properties, and the synthetic resin material itself forms a surface layer, it may be unable to withstand long-term use due to poor surface scratch resistance and weather resistance.
[0004]
In addition, the window material obtained by the method (2) is poor in scratch resistance because the hydrophilic polymer absorbs moisture and becomes soft, and the hydrophilic polymer absorbs and releases moisture. Therefore, there is a problem in weather resistance. Further, the surfactant is released after long-term use, and the antifogging property may be lowered.
The window material obtained by the method (3) has a problem in long-term use because the synthetic resin film itself forms a surface layer and is poor in scratch resistance and weather resistance.
The best way to solve these problems is to apply a conductive paste to the surface of the synthetic resin window material and harden it, and adjust the resistance value to ensure the amount of heat generation necessary to demonstrate the anti-fogging function. Baking into a pattern (specifically, adjusting the thickness, width, length, number, etc. of the heating wire), and then over the entire surface of the synthetic resin window material coated with the conductive paste This is a method of forming a hard coat film.
[0005]
[Problems to be solved by the invention]
However, in the method of forming a hard coat film on the entire surface of the resin window material on which the conductor paste is applied as a pattern of heating lines, it has good adhesion to synthetic resin articles and has heat resistance and weather resistance. In addition, a conductive paste capable of realizing a low resistance value capable of securing a calorific value necessary for exhibiting an anti-fogging function, a synthetic resin article, and an improvement in wear resistance of the conductive paste Even if it comes into contact with the hard coat solution, the paste part will not be eroded, no whitening will occur, and a combination with a hard coat agent that can maintain good adhesion and weather resistance has not been obtained. A method for forming a hard coat film on the entire surface of a resin window material on which body paste is applied as a pattern of heating lines has not been put to practical use.
An object of the present invention is to produce a synthetic resin article having antifogging performance, and not only exhibit antifogging performance for a long period of time, but also have a scratch resistance and weather resistance that should originally be provided.Vehicle window materialIs to provide.
Another object of the present invention is to provide a synthetic resin having anti-fogging performance without any problems such as elution of the conductive paste during hard coat application and peeling of the conductive paste from the synthetic resin article.Vehicle window materialIs to manufacture.
[0006]
[Means for Solving the Problems]
  The above object of the present invention is achieved by the following configuration.
  That is, polycarbonate resin plate, acrylic resinBoard (A) on (1) saturated polyester resin, (2) mixture of saturated polyester resin and vinyl chloride resin, (3) mixture of saturated polyester resin and vinyl chloride-vinyl acetate copolymer resin, or (4) saturated polyester resin and chloride. An exothermic pattern layer (B) formed using a conductive paste containing a binder resin comprising a mixture of vinyl resin and vinyl chloride-vinyl acetate copolymer resin, a conductivity-imparting agent and a solvent, and the pattern layer (B) It consists of a silicone-based hard coat layer (D) formed on the topFor vehiclesAnti-fogging coating synthetic resinMadeIt is a window material.
  Of the present inventionFor vehiclesAnti-fogging coating synthetic resinMadeA copolymer of an acrylic resin or an acrylic monomer and another monomer copolymerizable therewith between the exothermic pattern layer (B) of the window material and the silicone hard coat layer (D)-The structure which formed the acrylic-type solvent-type undercoat (C) to contain may be sufficient.
  In addition, the present inventionFor vehiclesAnti-fogging coating synthetic resinMadeThe exothermic pattern layer (B) of the window material can be composed of a plurality of rows of heating lines and a pair of electrode portions provided at both ends of the rows of heating lines.
[0007]
  In addition, the present inventionAn anti-fogging coating synthetic resin window material for vehicles can be manufactured by the following method.
  (1) a saturated polyester resin, (2) a mixture of a saturated polyester resin and a vinyl chloride resin on an acrylic resin plate (A) coated with a polycarbonate resin plate, an acrylic resin plate or a polycarbonate resin film, (3) Mixture of saturated polyester resin and vinyl chloride-vinyl acetate copolymer resin or (4) Binder resin composed of a mixture of saturated polyester resin, vinyl chloride resin and vinyl chloride-vinyl acetate copolymer resin, conductivity imparting agent and solvent A body paste is applied and cured to apply an exothermic pattern layer (B) and cured, and a silicone-based hard coat layer (D) is applied to the pattern layer (B) and cured.Consists of.
  Made aboveManufacturing methodInAfter forming the exothermic pattern layer (B), a copolymer of an acrylic resin or acrylic monomer and another monomer copolymerizable therewith on the pattern layer (B)-Apply and harden the acrylic solvent type undercoat layer (C) to be contained, and then apply and harden the silicone hard coat layer (D) on the undercoat layer (C).WhoIs the law.
  Of the present inventionFor vehiclesAnti-fogging coating synthetic resinMadeThe silicone hard coat layer of the window material is
    RSi (OH)_Three
    R represents an alkyl group having 1 to 3 carbon atoms, a vinyl group, a 3, 3, 3-trifluoropropyl group, a γ-aminopropyl group, a γ-methacryloxypropyl group, and a γ-glycid. Selected from the group consisting of xyloxy groups.
And a water or alcohol dispersion of colloidal silica or other colloidal metal oxide,Colloidal silica consisting ofOr other colloidal metal oxideIt is preferable to form from containing organopolysiloxane.
[0008]
  Hereinafter, the antifogging coating component and the like will be described in detail.
1. Structure of conductor paste that demonstrates anti-fogging function
(1)Resin used as binder
  As the binder resin, an acrylic resin, an epoxy resin, a phenol resin, a polyester resin, or the like can be used, but a polyester resin is most preferable. The reason is(I)Because it is easy to disperse silver powder and copper powder, the paste with the lowest resistance is obtained.(B)Excellent adhesion to polycarbonate resin, acrylic resin, etc.(C)Possesses good heat resistance,(D)Has good weather resistance.(E)This is because it has excellent solvent resistance.
  Examples of the polyester resin used as the binder resin of the present invention include an aromatic carboxylic acid (for example, phthalic acid, trimellitic acid, etc.) and an aliphatic carboxylic acid (for example, maleic acid, succinic acid, etc.) for imparting flexibility. A saturated polyester resin composed of a dibasic acid and a glycol (for example, polyethylene glycol, polypropylene glycol, etc.), which is a mixture of acids, etc., and its molecular weight is preferably 5,000 to 40,000, more preferably 10,000 to 30. , 000. When the molecular weight is too low, the solvent resistance and heat resistance are lowered, and when the molecular weight is too high, dispersion of silver powder, copper powder and the like is difficult and the resistance value becomes high.
[0009]
Moreover, it is possible to use a polyester resin alone as the binder resin, a saturated polyester resin, a mixture of a saturated polyester resin and a vinyl chloride resin, and / or a vinyl chloride and 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 the crosslinking agent in the saturated polyester resin is preferably 0 to 20% by weight (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). In addition, when it is necessary to improve the solvent resistance especially for high boiling point ether and alcohol solvents used at the time of hard coating or primer coating, a mixture of vinyl chloride resin or vinyl chloride / vinyl acetate copolymer resin and It is preferable to include an isocyanate or a blocked isocyanate as a crosslinking agent.
[0010]
(2)Conductivity imparting agent
  Conductive metal powder such as silver powder is used. The metal powder is preferably subjected to a surface treatment (effective as a lubricant) with a long-chain organic acid such as stearic acid to improve dispersibility. The shape of the conductivity-imparting agent is preferably flaky. In the case of flaky, a fine size having a diameter of about 1 to 30 μm and a thickness of about 3 to 5 μm is preferable.
  In addition to silver powder, conductive metal powder such as copper or zinc powder can be used.
(3)solvent
  Although there is no particular limitation as long as the solubility is high and printability is not adversely affected, butyl cellosolve acetate, ethyl cellosolve acetate and the like, which are high-boiling solvents, are preferably used.
  The solid content of the conductor paste is(1)+(2)The range of 35 to 75% by weight is preferable. More preferably, it is 50 to 70% by weight. This is because when the solid content of the conductive paste is low, a low resistance value cannot appear, and when the solid content is high, the dispersibility of conductive metal powder such as silver powder is impaired.
[0011]
2. Optimum conditions for conductor paste thickness and curing conditions
200-800 W / m to develop the anti-fogging function on the surface of synthetic resin articles²Some degree of heat generation is required. Therefore, for example, in the synthetic resin window frame shown in FIG. 1, 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 conductive paste are set. By changing, a desired calorific value can be obtained. However, the film thickness of the electrode portions 1a and 1b and the heating wire 2 is preferably about 5 to 30 μm. More preferably, it is 10-20 micrometers.
When the film thickness of the electrode portions 1a, 1b and the heating wire 2 is 5 μm or less, a required resistance value cannot be obtained, and when it is 30 μm or more, the flexibility of the coating film of the conductor pattern constituting the heating wire 2 is lowered. In addition, cracks are easily generated and liquid dripping is likely to occur from the boundary portion during hard coating.
The conductive paste is cured at about 80 to 130 ° C. in order to eliminate the residual solvent as much as possible. However, the conductive paste is dried for a relatively long time in the low temperature range and shorter in the high temperature range. The curing time is preferably between about 20 minutes and 3 hours. If the drying is insufficient, the binder resin tends to be eluted or a sufficiently low resistance value cannot be obtained.
[0012]
3. Silicone hard coat material
Although not particularly limited, typical silicone hard coat agents as shown below can be preferably used.
RSi (OH)_Three
(Wherein R is an alkyl group having 1 to 3 carbon atoms, vinyl group, 3,3,3-trifluoropropyl group, γ-aminopropyl group, γ-methacryloxypropyl group and γ-glycidoxypropyl group) Selected from the group consisting of groups, preferably R is a methyl group or a γ-glycidoxypropyl group) and water or an alcohol dispersion of colloidal silica or other colloidal metal oxide. Colloidal silica-containing organopolysiloxane coating agent 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 adhesion on both the silicone-based hard coat agent and the synthetic resin material. An acrylic solvent type subbing layer containing a crosslinking agent and an ultraviolet absorber as needed is preferably used for a resin or a copolymer of an acrylic monomer and another monomer copolymerizable with an acrylic monomer.
[0013]
Further, when the synthetic resin article is a window, the peripheral portion of the synthetic resin window has a shielding property in order to improve the design by hiding the terminals or conductors connected to the electrode portions 1a and 1b from the outside of the window. Masking printing may be performed with ink. Such masking printing is usually performed before applying the conductor paste.
The exothermic 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 for a synthetic resin plate, a synthetic resin film, and a synthetic resin molded product. it can. For example, it can be used for windows for vehicles, windows for refrigerated storage, lighting windows in cold regions, 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 on the back surface as well as the front surface thereof.
[0014]
[Action]
  According to the present invention, a synthetic resin comprising a synthetic resin such as a polycarbonate resin or an acrylic resin.On the boardApply a pattern made of a conductive paste whose resistance value is adjusted so that the amount of heat generation necessary to provide an antifogging function can be secured by direct screen printing, etc., and then baked, and then from above this conductive pattern layer Since the hard coating can be applied without any problem, the surface of the synthetic resin article can be given anti-fogging property, and the conductor paste part, including the conductive paste part, can be scratched on the entire surface of the synthetic resin article. An improvement in weather resistance can be achieved. In addition, this saturated polyester resin-based conductive pattern layer has good adhesion to the surface of synthetic resin articles, has weather resistance, does not elute even when contacted with a silicone-based hard coat solution, and is subject to erosion. There is nothing. Furthermore, by selecting a conductive paste that can secure the heat generation necessary to provide an antifogging function, and combining the conductive paste with a silicone hard coat with good adhesion, scratch resistance, and weather resistance, antifogging and A coated synthetic resin article having good scratch resistance and weather resistance can be obtained. In addition, since the hard coating can be applied without any problem on the printed conductive paste as in the case of inorganic glass, the heating line portion patterned with the conductive paste and other portions are protected. It has become possible to finish the surface of a synthetic resin article having cloudiness with an excellent appearance.
[0015]
【Example】
Examples of the present invention will now be described.
Example 1
(Adjustment of undercoat)
While maintaining 320 g of propylene glycol monomethyl ether at 90 ° C. under a nitrogen atmosphere, a mixture of 90 g of methyl methacrylate, 10 g of γ-methacryloxypropyltrimethoxysilane, and 0.8 g of azobisisobutyronitrile was added over 2 hours. The same temperature was maintained for 5 hours. Thereafter, 760 g of ethyl cellosolve, 5 g of a 10% aqueous solution of di-n-butylamine, 1.1 g of diethylene glycol, and 20 g of 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole were added to obtain a base coating material A.
(Adjusting the top coat)
Colloidal silica (manufactured by Nissan Chemical Industries, trade name Snowtex O-40, water dispersion type, solid content 40%) 135 g and colloidal antimony oxide (manufactured by Nissan Chemical Industries, trade name: antimony oxide sol 1510P, water (Dispersion type, solid content: 12%) 207 g of methyltrimethoxysilane and 7.0 g of acetic acid are added to 110 g, and the mixture is stirred for 3 hours while maintaining the temperature at 50 ° C. to perform hydrolysis. Thereafter, 195 g of n-butanol, 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 material A.
[0016]
(Formation of automotive window materials)
Conductor paste A (manufactured by Fujikura Kasei Co., Ltd., trade name Dotite FA-323, binder resin is a saturated polyester resin on the surface of a pre-cleaned polycarbonate plate (made by Tsutsunaka Plastic Industry Co., Ltd., trade name Polycaace), A type in which the cross-linking agent is plock isocyanate, specific resistance 3.5 × 10^-FiveΩcm) is screen-printed, and a plurality of heating lines with a line width of 1.0 mm arranged in parallel with a line interval of 15 mm and a pair of electrode portions with a width of 20 mm are applied to the left and right ends of these heating lines. The conductor paste was cured by heating for 45 minutes to obtain a heating line pattern layer.
The polycarbonate plate with a heating wire was heated at 180 ° C. for 10 minutes, and automotive window material A was formed by hot press bending.
[0017]
The undercoat paint A was applied to the automotive window material A with a 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 wire portion was not eroded by the undercoat paint A, and a clean coated surface was obtained without any eluted components.
Next, the above-mentioned top coating material A is applied to the polycarbonate automobile window material A coated with the undercoat layer thus obtained by a dipping method, and is cured by heating and drying in a hot air drying oven at 120 ° C. for 60 minutes. I let you. Also at this time, the printed surface portion of the heating wire portion was not eroded and a clean coated surface was obtained without elution.
The coated automotive window material A with a heating wire thus obtained has a transparent and clean coated surface, and both the heating wire portion and the transparent portion have wear resistance A, adhesion 100/100, and water resistance. Furthermore, the appearance, hardness and adhesion after 2000 hours of the sunshine weatherometer test were also good. Moreover, anti-fogging property has confirmed that cloudiness became completely clear within 10 minutes (after 6-7 minutes) after electricity supply.
[0018]
In addition, the evaluation method of the coating film was performed with the following method.
Abrasion resistance: rubbed with # 0000 steel wool and examined for resistance to scratching, and judged as follows.
A: Even if it rubs strongly, it is not damaged.
B: Slightly scratched when rubbed strongly.
C: Even a weak friction can be scratched.
Adhesiveness: In the so-called cross-cut tape test, after cross-cutting 100 squares by putting 11 parallel lines vertically and horizontally at 1 mm intervals on the painted surface with a knife, and attaching cellophane adhesive tape on it, The tape was peeled off and displayed as the number of squares that did not peel out of the 100 squares.
Water resistance: after standing in warm water at 60 ° C. for 7 days, check for abnormalities such as whitening of the film, cracks or peeling.
Accelerated weather resistance test: Weather resistance was evaluated by a sunshine carbon arc weatherometer. The black panel temperature was 63 ± 3 ° C., and water spraying was performed at a cycle of 12 minutes / hour. The xenon arc weatherometer was also evaluated for weather resistance. The black panel temperature is 63 ± 3 ° C. Water spray is a cycle of 18 minutes / 2 hours, and the irradiation intensity is 0.35 W / m at 340 nm.²It carried out in.
Next, the measurement method of anti-fogging property was performed by the following method.
A window made of synthetic resin with a heating wire is attached to a passenger car, placed in an environment with an outside temperature of 0 ° C, an inside temperature of 30 ° C, and an inside humidity of 80% RH. And time until cloudy weather was cleared was measured.
[0019]
Example 2
(Adjusting the top coat)
80 g of γ-glycidoxypropyltrimethoxysilane, 144 g of methyltrimethoxysilane, 71 g of colloidal silica (trade name Snowtex O, water dispersion type, solid content 20%, manufactured by Nissan Chemical Industries, Ltd.) and 0.1N hydrochloric acid aqueous solution 170 g was mixed and hydrolyzed by stirring for 2 hours while maintaining at 80 ° C. 146 g of ethyl cellosolve and 1.3 g of ammonium perchlorate were added to the ternary cohydrolyzate solution thus obtained to obtain a top coating material B.
Conductor paste B (made by Fujikura Kasei Co., Ltd., Dotite FA-517 (trade name), binder resin is saturated polyester resin on the surface of a previously cleaned acrylic plate (Sumitomo Chemical Co., Ltd., trade name Sumipex) Type consisting of a mixture of vinyl chloride / vinyl acetate copolymer resin, specific resistance 3.0 × 10^-FiveΩcm) is screen-printed, a plurality of heating lines having a line width of 1.5 mm arranged in parallel with a line interval of 20 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 for 2 hours.
[0020]
The acrylic plate with a heating wire was heated at 140 ° C. for 10 minutes, and an automobile window material B was formed by a vacuum forming method.
The top coating material B was applied by flow coating (flow coating method) to the automotive window material B with a heating wire, and dried by heating at 80 ° C. for 3 hours in a hot air drying furnace. At this time, there was no change in the printed surface portion of the heating line portion, and a clean coated surface was obtained without whitening due to elution.
The automotive window material B with a heating wire thus obtained has a transparent and clean coat surface, and both the heating wire portion and the transparent portion have wear resistance A, adhesion 100/100, and water resistance are also good. Furthermore, the appearance, hardness and adhesion after 2000 hours of the sunshine weatherometer test were also good. Further, the antifogging property was confirmed to be completely cloudy within 10 minutes (after 5 to 6 minutes) after energization.
[0021]
  Reference exampleandreferenceComparative Examples 1 and 2
  This reference example is not an example of the present invention.
  Screen printing was performed on a pre-cleaned polycarbonate film (product name: Polyca ace, 0.5 mm thickness, manufactured by Tsutsunaka Plastic Industry Co., Ltd.) using an acrylic black masking ink, dried at 120 ° C. for 10 minutes, and rear win A colored shielding part having a width of 40 mm was formed on the peripheral part of the shape corresponding to the dough. Further, on the colored shielding part, the same conductive paste A as in Example 1 was used to screen-print the same heating line pattern as in Example 1 and heated at 120 ° C. for 45 minutes to cure the conductive paste. . At this time, the same heat generating line pattern was screen-printed on the colored shielding part using a conductive paste of a phenolic resin and an epoxy resin as shown in Table 1 by the same method at 120 ° C. The conductor paste was cured by heating for 45 minutes.
[0022]
[Table 1]

[0023]
The polycarbonate film with a heating wire made of different conductive pastes with colored shielding portions is cut into a window material shape and attached to an injection mold, and a heat-resistant acrylic resin (KAMAX T-240 manufactured by Rohm & Haas) is applied. Various window materials C were prepared by injection and so-called film insert molding.
The undercoating paint A prepared in Example 1 was applied to the various window materials C produced by the above molding method by a dipping method, followed by heat drying at 120 ° C. for 60 minutes in a hot air drying furnace.
The topcoat paint A prepared in Example 1 was applied to the polycarbonate film insert heat-resistant acrylic window material C coated with the obtained undercoat layer by a dipping method, and was dried by heating in a heating drying oven at 120 ° C. for 60 minutes to be cured.
The window material C using the conductive paste A among the various heat-resistant acrylic coated window materials C with the colored shielding portion and the heating wire thus obtained is transparent and has a clean coated surface. The part and the transparent part both had abrasion resistance A, adhesion 100/100, good water resistance, and good appearance, hardness and adhesion after 2000 hours of xenon weatherometer test. Further, the anti-fogging performance was confirmed to be completely cloudy within 10 minutes after energization (after 6 to 7 minutes). However, it was confirmed that the window material C using another conductive paste caused exfoliation of exothermic lines, and the antifogging performance was not completely clouded even after 20 minutes had passed after energization.
[0024]
Example 4 and Comparative Examples 3 and 4
(Adjustment of undercoat)
A solution prepared by dissolving 1.0 g of azobisisobutyronitrile in 200 g of propylene glycol monomethyl ether while maintaining a mixture of 400 g of propylene glycol monomethyl ether, 170 g of methyl methacrylate and 30 g of 2-hydroxyethyl methacrylate at 80 ° C. in a nitrogen atmosphere. Was added over 2 hours and kept at the same temperature for an additional 5 hours. Thereafter, 400 g of propylene glycol monomethyl ether and 21 g of 2- (2′-hydroxy-5′-octylphenyl) benzotriazole were added to prepare an undercoat paint B.
(Adjusting the top coat)
Colloidal silica (manufactured by Nissan Chemical Industries, trade name Snowtex O-40, water dispersion type, solid content 40%) 150 g, colloidal antimony oxide (manufactured by Nissan Chemical Industries, Ltd., trade name Sun Colloid AMT-130S, Alcohol-dispersed solid content (30% solid) was added to 220 g of methyltrimethoxysilane and 10 g of acetic acid, and the mixture was stirred for 2 hours while maintaining the temperature at 55 ° C. for hydrolysis. Thereafter, 250 g of isopropyl alcohol, 200 g of n-butanol, 1.3 g of sodium acetate and 11 g of acetic acid were added to obtain a top coating material C.
[0025]
(Window material with heating wire)
Conductor paste C (made by Fujikura Kasei Co., Ltd., trade name Dotite FA-333, binder resin) is formed on the surface of the window material D that is injection-molded using a heat-resistant acrylic resin (trade name Delmore H350A, manufactured by Asahi Kasei Co., Ltd.). Saturated polyester resin single type, specific resistance 3.0 × 10^-FiveA 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 for a minute.
At this time, the conductor paste C was screen-printed on the window material D by the same method, a similar heating line pattern was created, and cured at each drying temperature and time of Comparative Examples 3-4.
The undercoat paint C was applied to the window material D with a heating wire having different drying conditions by a dipping method and dried for 30 minutes, and then the top coat C was applied by a dipping method and dried by heating at 110 ° C. for 60 minutes to be cured. .
The window material D thus obtained is as shown in Table 2, and when the drying temperature is too low or the drying time is too short and the drying is insufficient, the conductive paste is eluted and whitened, or the conductive paste is Defects such as erosion by the solvent of the coating liquid and floating occurred.
[0026]
[Table 2]

[0027]
【The invention's effect】
According to the present invention, the heat generation pattern layer using the conductor pasteCompositionresinVehicle window materialCan exhibit anti-fogging properties andCompositionresinVehicle window materialImprovement of scratch resistance and weather resistance can be achieved by the hard coat layer made of silicon resin formed on the entire surface.
[Brief description of the drawings]
FIG. 1 is a diagram for explaining a pattern of heating lines and electrode portions using a conductive paste formed on a synthetic resin article according to an embodiment of the present invention.
[Explanation of symbols]
1 ... electrode part, 2 ... heating wire

Claims (4)

(1) Saturated polyester resin, (2) Mixture of saturated polyester resin and vinyl chloride resin, (3) Saturated polyester resin and vinyl chloride-vinyl acetate copolymer resin on polycarbonate resin plate, acrylic resin plate ( A) (4) Exothermic pattern layer formed by using a conductive paste containing a binder resin, a conductivity-imparting agent, and a solvent comprising a mixture or (4) a saturated polyester resin, a vinyl chloride resin, and a vinyl chloride-vinyl acetate copolymer resin. B) and
The pattern layer (B) formed on a silicone based hard coat layer (D) and vehicle anti-fogging, characterized in that consists of coating a synthetic resin window material. The heating pattern layer (B) and a silicone hard coat layer (D) and acrylic solvent type subbing layer containing a copolymer chromatography with acrylic resin or an acrylic monomer copolymerizable therewith other monomers during the ( The window material made of anti-fogging coating synthetic resin for vehicles according to claim 1, wherein C) is formed. 2. The antifogging coating synthetic resin for vehicles according to claim 1, wherein the exothermic pattern layer (B) comprises a plurality of rows of heating lines and a pair of electrode portions provided at both ends of the plurality of rows of heating wires. Ltd. window material. The silicone-based hard coat layer (D) has the following formula: RSi (OH) ₃
(R is an alkyl group having 1 to 3 carbon atoms, a vinyl group, a 3,3,3-trifluoropropyl group, a γ-aminopropyl group, a γ-methacryloxypropyl group, and a γ-glycidoxypropyl group. Selected from the group of
Claim to a partial condensate of, characterized in that it is formed with water or an alcohol dispersion of colloidal silica or other colloidal metal oxides, from colloidal silica or other colloidal metal oxide-containing organopolysiloxane consisting of 1 The window material made from anti-fogging coating synthetic resin for vehicles in any one of -3.

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