JP4409890B2 - Condensation pattern formation method for glass products - Google Patents
Condensation pattern formation method for glass products Download PDFInfo
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- JP4409890B2 JP4409890B2 JP2003318693A JP2003318693A JP4409890B2 JP 4409890 B2 JP4409890 B2 JP 4409890B2 JP 2003318693 A JP2003318693 A JP 2003318693A JP 2003318693 A JP2003318693 A JP 2003318693A JP 4409890 B2 JP4409890 B2 JP 4409890B2
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- 239000011521 glass Substances 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 33
- 238000009833 condensation Methods 0.000 title claims description 15
- 230000005494 condensation Effects 0.000 title claims description 15
- 230000007261 regionalization Effects 0.000 title 1
- 239000005871 repellent Substances 0.000 claims description 47
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000463 material Substances 0.000 description 21
- 230000002940 repellent Effects 0.000 description 15
- 238000007639 printing Methods 0.000 description 11
- 230000000873 masking effect Effects 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 238000007649 pad printing Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- -1 alkylsilane compounds Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 235000020965 cold beverage Nutrition 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Surface Treatment Of Glass (AREA)
Description
本発明は、ガラス表面の無色透明の絵柄が、常温ではほとんど視認することができないものであるが、空気中で冷却されると細かい結露によって絵柄を発現せしめる結露絵柄ガラス製品に関するものである。意匠性・装飾性を目的とする装飾ガラス製品で、特にコップ等のガラス食器、ボトル等の包装用容器などに有用である。 The present invention relates to a dew-pattern glass product that allows a colorless and transparent pattern on a glass surface to be hardly visually recognized at room temperature, but allows the pattern to be expressed by fine dew condensation when cooled in air. It is a decorative glass product for the purpose of design and decoration, and is particularly useful for glass tableware such as cups and packaging containers such as bottles.
従来から、自動車のフロントガラスやサイドガラスなどのガラス表面には撥水膜層を形成することにより撥水処理がなされている。その際の撥水膜層を形成するものとして、フルオロアルキルシランやフッ素樹脂などが使用されてきた（たとえば、特許文献１参照）。また、ガラス基板やガラスコップなどの表面に撥水膜層によって模様などを構成することで装飾効果を目的とするものもある（たとえば、特許文献２および３参照）。これらの撥水膜層にも上記と同様フルオロアルキルシラン系化合物、アルキルシラン系化合物、フッ素樹脂系化合物が開示されている（たとえば、特許文献３参照）。さらに、ガラス表面への膜付け法として、ノズルフローコート法、ディッピング法、スプレー法、リバースコート法、フレキソ法、印刷法、フローコート法などが既知の塗布手段として開示されている（たとえば、特許文献３参照）。そして、模様のパターニングの方法としてはカッティングプロッター、レーザー光等によって模様を切り抜く方法やマスキング材を貼り付ける方法等がある。これに、撥水性、耐久性を向上させるためにＳｉＯ2系の透明なゾルゲル膜をアンダーコートする方法も記載されている（たとえば、特許文献２参照）。
これらの従来技術の中から「印刷」によって撥水膜を形成する方法に着目すると、ガラス表面に通常のガラス用焼付インクによって色絵柄をつける公知の印刷方法には、スクリーン印刷、パッド印刷などがあるが、撥水材料を含有したインクによって絵柄を印刷する場合には、上記の公知方法を用いることができなかった。なぜなら、撥水材料として知られるフルオロアルキルシラン、テフロン（登録商標）などのフッ素含有材料およびシリコーン樹脂においては、撥水材料をガラスと結合させるために行う熱処理時に、撥水性物質が絵柄部以外の周辺へ蒸着してしまうからである。すなわち、上記の公知の印刷方法ではガラス全面が撥水化してしまい、絵柄部のみを印刷することができなかった。 Focusing on the method of forming a water-repellent film by “printing” from among these conventional techniques, known printing methods for applying a color pattern to a glass surface with ordinary glass baking ink include screen printing and pad printing. However, in the case where a pattern is printed with an ink containing a water repellent material, the above known method cannot be used. This is because, in fluorine-containing materials such as fluoroalkylsilane and Teflon (registered trademark), which are known as water repellent materials, and silicone resins, the water repellent material other than the pattern portion is subjected to heat treatment to bond the water repellent material to glass. This is because it will be deposited on the periphery. That is, with the above-described known printing method, the entire glass surface becomes water repellent, and only the pattern portion cannot be printed.
したがって、撥水材料を含有したインクによって絵柄を印刷する場合には、（１）撥水材料含有インクを全面に塗布して熱処理後に絵柄部をマスキング材で印刷し、フッ酸で非マスク部を除去して、最後にマスクを除去する方法、または（２）抜き絵柄のマスクを印刷後、撥水材料含有インクを塗布して熱処理後にマスクを除去する方法が用いられている。しかしこれらの方法は、マスキングを行う必要があるため、通常のインクによって色絵柄をつける公知の印刷方法に比べてはるかに手間とコストを要するものであった。また、フッ素含有材料を用いた撥水膜については、アルカリ洗浄に対する耐性がないという欠点もあった。 Therefore, when printing a pattern with an ink containing a water repellent material, (1) applying the water repellent material containing ink on the entire surface, printing the pattern portion with a masking material after heat treatment, and removing the non-mask portion with hydrofluoric acid. A method of removing and finally removing the mask, or (2) a method of removing the mask after heat treatment by applying a water-repellent material-containing ink after printing a mask with a blank pattern is used. However, since these methods require masking, they are much more laborious and costly than known printing methods in which a color pattern is applied with ordinary ink. In addition, the water-repellent film using a fluorine-containing material has a drawback that it is not resistant to alkali cleaning.
一方、コップのようなガラス食器においては、出荷時に、商標、模様、文字などが印刷された意匠性のあるラベルが外周面に貼られることが多い。ラベル材質はＰＥＴラベルなどの透明なものや紙ラベルなどの不透明なもの等が使われている。しかし、コップのユーザーは、コップ購入後、ラベルを剥がしてコップを使用するため、ラベルに印刷された商標、模様、文字などはコップ使用時には失われていた。 On the other hand, in a glass tableware such as a cup, a label having a design property on which a trademark, a pattern, a character, and the like are printed is often attached to the outer peripheral surface at the time of shipment. As the label material, a transparent material such as a PET label or an opaque material such as a paper label is used. However, since the cup user peels off the label and uses the cup after purchasing the cup, the trademark, pattern, characters, etc. printed on the label are lost when the cup is used.
本発明は、ガラス表面に無色透明撥水性膜層を形成する過程と、熱処理により該撥水性膜層をガラス表面に固定する熱処理過程によりガラス表面に無色透明撥水性膜層からなる絵柄を形成するガラス製品の結露絵柄形成方法であって、前記撥水性膜層が、前記熱処理過程の際に、前記絵柄部を形成する撥水性物質が揮発し、前記絵柄部以外のガラス表面に再付着しないウレタン、アクリルシリコーンまたはメラミンでなり、前記熱処理過程においてマスキングを行わないことを特徴とするガラス製品の結露絵柄形成方法である。
The present invention forms a pattern comprising a colorless and transparent water-repellent film layer on a glass surface by a process of forming a colorless and transparent water-repellent film layer on the glass surface and a heat treatment process of fixing the water-repellent film layer to the glass surface by heat treatment. A dew pattern forming method for glass products, wherein the water repellent film layer is a urethane in which the water repellent material forming the pattern part is volatilized during the heat treatment process and does not reattach to the glass surface other than the pattern part. A method for forming a dew pattern on a glass product, characterized in that it is made of acrylic silicone or melamine and is not masked in the heat treatment process .
無色透明撥水性膜層からなる絵柄を形成するガラス製品は、常温では当該膜層からなる無色透明絵柄はほとんど視認することができないが、冷たい飲料等を注ぐと空気中の水蒸気がコップの外表面に結露し、絵柄を視認することができるものである。この様子を図１に示す。絵柄部２は無色透明撥水性膜層からなっている。また、この原理を説明する図が図２である。図２は図１のガラスコップの断面部分拡大図である。ガラス表面１３上に無色透明撥水性膜層１０が形成されており、該撥水性膜層１０（絵柄部）上の結露水１１は非常に細かく、光の乱反射を受ける。これに対して、該撥水性膜層１０以外のガラス表面（非絵柄部）上の結露水１２は大きく、光の乱反射は受けていない。すなわち、該撥水性膜層からなる絵柄部は、水の接触角が大きく、非絵柄部と異なり結露が非常に細かいので、冷却時のこの細かい結露水が光に乱反射することにより絵柄が白く浮き出るように見えるのである。 A glass product that forms a pattern consisting of a colorless and transparent water-repellent film layer can hardly see the colorless and transparent pattern that consists of the film layer at room temperature. Condensation can occur and the pattern can be visually recognized. This is shown in FIG. The pattern part 2 consists of a colorless and transparent water-repellent film layer. FIG. 2 is a diagram for explaining this principle. FIG. 2 is an enlarged partial cross-sectional view of the glass cup of FIG. A colorless and transparent water-repellent film layer 10 is formed on the glass surface 13, and the condensed water 11 on the water-repellent film layer 10 (pattern part) is very fine and receives irregular reflection of light. On the other hand, the dew condensation water 12 on the glass surface (non-picture part) other than the water repellent film layer 10 is large and is not subjected to irregular reflection of light. That is, the pattern portion made of the water-repellent film layer has a large water contact angle and, unlike the non-pattern portion, the dew condensation is very fine. It looks like this.
本発明は、前記撥水性膜層として、熱処理過程の際に、ガラス表面の絵柄部以外の部分（非絵柄部）に撥水性物質が蒸着しないものを用いることにより、スクリーン印刷やパッド印刷のような公知の印刷方法で印刷しても、絵柄部のみを的確に印刷することができる。したがって、本発明によれば従来のようなマスキングの必要がなくなる。 In the present invention, as the water-repellent film layer, a layer in which a water-repellent substance is not deposited on a portion other than the pattern portion (non-pattern portion) on the surface of the glass during the heat treatment process is used. Even if printing is performed by any known printing method, only the pattern portion can be printed accurately. Therefore, according to the present invention, conventional masking is not necessary.
該撥水性膜層には、撥水材料としてウレタン、アクリルシリコーンまたはメラミンを用いるのが好ましい。これらは、フルオロアルキルシラン、テフロン（登録商標）、シリコーンなど公知の撥水材料に比べて撥水性がやや小さい場合もあるが、水の接触角は、親水性であるガラス表面の非絵柄部とは大差があるため、結露絵柄を発現させる目的は十分に達成できる。なお、ウレタン、アクリルシリコーンまたはメラミンを用いた場合でも、熱処理時における蒸着の可能性を防ぐため、樹脂の硬化およびガラスとの結合に必要な最低温度までの昇温に留め、必要ならば硬化促進剤を添加するのが好ましい。 In the water repellent film layer, it is preferable to use urethane, acrylic silicone or melamine as a water repellent material. These may have slightly smaller water repellency than known water-repellent materials such as fluoroalkylsilane, Teflon (registered trademark), and silicone, but the contact angle of water is different from the non-patterned portion of the glass surface that is hydrophilic. Since there is a large difference, the purpose of expressing the condensation pattern can be sufficiently achieved. Even when urethane, acrylic silicone or melamine is used, to prevent the possibility of vapor deposition during heat treatment, the temperature is raised to the minimum temperature required for resin curing and bonding with glass, and curing is accelerated if necessary. It is preferable to add an agent.
冷却前の無色透明絵柄をより視認されにくくするために、スクリーン印刷の場合は望ましくは２５０メッシュ以上の細かいメッシュ、パッド印刷の場合は望ましくは５０μ以下の浅いセルを用いて樹脂膜厚を薄くするのが好ましい。 In order to make the colorless and transparent pattern before cooling more difficult to see, the resin film thickness is reduced by using a fine mesh of preferably 250 mesh or more for screen printing and a shallow cell of 50 μm or less for pad printing. Is preferred.
このように、本発明によれば、面倒なマスキング作業が不要になり、従来の印刷方法であるスクリーン印刷またはパッド印刷のみで絵柄部のみに的確に無色透明撥水性膜層を形成することができる。生産コストもマスキングが不要なため従来法の１／３以下になった。さらに、結露絵柄は常温では無色、冷却時には白く浮き出るものであるため、食器ガラスにおけるエッチング加工のような高級装飾に比肩する上品さがあり、また隠れ絵が現出することを楽しみながら冷たい飲料を味わうこともできる。加えて、本発明の無色透明撥水性樹脂は結露効果が食器洗浄機によるアルカリ洗浄にも耐性があり、業務用の食器ガラスにも繰り返し使用できる。 As described above, according to the present invention, a troublesome masking operation is not required, and a colorless and transparent water-repellent film layer can be accurately formed only on the pattern portion only by screen printing or pad printing, which is a conventional printing method. . Production cost masking becomes 1/3 or less of the unnecessary for the conventional method. In addition, the condensation pattern is colorless at room temperature and white when it cools, so it has an elegance comparable to luxury decoration such as etching processing on tableware glass, and you can enjoy a cold drink while enjoying the appearance of a hidden picture You can also taste it. In addition, the colorless and transparent water-repellent resin of the present invention has a dew condensation effect and is resistant to alkaline cleaning by a dishwasher, and can be used repeatedly for commercial tableware glass .
＜ウレタン樹脂＞
無色透明撥水性膜層としてウレタン樹脂を用いた本発明のガラス製品の実施例１を以下の通り作製し、撥水物の蒸着がないか等を調べた。
<Urethane resin>
Example 1 of the glass product of the present invention using a urethane resin as a colorless and transparent water-repellent film layer was prepared as follows, and it was examined whether or not water-repellent material was deposited.
十条ケミカル社製のウレタン樹脂を主剤とする１液熱硬化型インク（商品名ＭＩＧ−Ｎ２５００無色透明）に溶剤３０％、反応促進触媒２％、添加剤０．５％を加えて、直径６０ＭＭのガラスコップに３０ＭＭ×３０ＭＭ寸法の絵柄をスクリーン（３８０メッシュ）印刷後、１５０℃×５分の熱処理を行ったところ、非絵柄部への撥水物の蒸着はなかった。 A one-component thermosetting ink (trade name: MIG-N2500 colorless and transparent) based on urethane resin manufactured by Jujo Chemical Co., Ltd., with 30% solvent, 2% reaction promoting catalyst and 0.5% additive, When a 30 MM x 30 MM pattern was printed on a glass cup with a screen (380 mesh), and heat treatment was performed at 150 ° C for 5 minutes, no water-repellent material was deposited on the non-pattern portion.
常温では絵柄は視認されにくく、コップを透かして見ると絵柄の輪郭だけが白く視認された。コップに氷水を入れた冷却により、絵柄部には細かい結露が見られ、約１ＭＭの太さの線も認識できた。さらに、アルカリ耐性を調べるために、食器洗浄機によるアルカリ洗浄を５００回繰り返したが、透明絵柄の劣化や結露性の変化はなかった。上記の効果はスクリーン印刷に代えてパッド印刷を行い、同様な熱処理を行うことでも得られた。 The pattern was difficult to see at room temperature, and when looking through the cup, only the outline of the pattern was visible in white. By cooling with ice water in the cup, fine dew condensation was seen in the pattern, and a line with a thickness of about 1 MM could be recognized. Furthermore, in order to investigate the alkali resistance, the alkali washing by the dishwasher was repeated 500 times, but there was no deterioration of the transparent pattern and no change in dew condensation. The above effect was also obtained by performing pad printing instead of screen printing and performing the same heat treatment.
＜アクリルシリコーン樹脂＞
無色透明撥水性膜層としてアクリルシリコーン樹脂を用いた本発明のガラス製品の実施例２を以下の通り作製し、撥水物の蒸着がないか等を調べた。
<Acrylic silicone resin>
Example 2 of the glass product of the present invention using an acrylic silicone resin as a colorless and transparent water-repellent film layer was prepared as follows, and it was examined whether water-repellent material was deposited.
ナトコ社製のアクリルシリコーン樹脂を主剤とする１液熱硬化型インクに溶剤１５％を加えて、直径６０ＭＭのガラスコップに３０ＭＭ×３０ＭＭ寸法の絵柄をスクリーン（３８０メッシュ）印刷後、１５０℃×６０分の熱処理を行ったところ、非絵柄部への撥水物の蒸着はなかった。 15% solvent is added to a one-component thermosetting ink based on acrylic silicone resin manufactured by NATCO, and a 30MM x 30MM size pattern is printed on a screen (380 mesh) on a glass cup with a diameter of 60MM. As a result, no water-repellent material was deposited on the non-pattern part.
常温では絵柄は視認されにくく、コップを透かしてみると絵柄の輪郭だけが白く視認された。コップに氷水を入れた冷却により、絵柄部には細かい結露が見られ、約１ＭＭの太さの線も認識できた。さらに、アルカリ耐性を調べるために、食器洗浄機によるアルカリ洗浄を５００回繰り返したが、透明絵柄の劣化や結露性の変化はなかった。 The pattern was difficult to see at room temperature, and when looking through the cup, only the outline of the pattern was visible in white. By cooling with ice water in the cup, fine dew condensation was seen in the pattern, and a line with a thickness of about 1 MM could be recognized. Furthermore, in order to investigate the alkali resistance, the alkali washing by the dishwasher was repeated 500 times, but there was no deterioration of the transparent pattern and no change in dew condensation.
＜メラミン樹脂＞
無色透明撥水性膜層としてメラミン樹脂を用いた本発明のガラス製品の実施例３を以下の通り作製し、撥水物の蒸着がないか等を調べた。
<Melamine resin>
Example 3 of the glass product of the present invention using a melamine resin as a colorless transparent water-repellent film layer was prepared as follows, and it was examined whether or not water-repellent material was deposited.
メラミン樹脂においても、上記実施例１のウレタン樹脂と同様の調合・同様のプロセスで同様の結果が得られた。 Also for the melamine resin, the same result was obtained by the same preparation and the same process as the urethane resin of Example 1 above.
１ ガラスコップ
２ 絵柄部
１０ 無色透明撥水性膜層
１１ 結露水
１２ 結露水
１３ ガラス表面
DESCRIPTION OF SYMBOLS 1 Glass cup 2 Pattern part 10 Colorless transparent water-repellent film layer 11 Condensation water 12 Condensation water 13 Glass surface
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| JP2003318693A JP4409890B2 (en) | 2003-09-10 | 2003-09-10 | Condensation pattern formation method for glass products |
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| JP2009010972A Division JP2009078974A (en) | 2009-01-21 | 2009-01-21 | Glass product with pattern developed by dew condensation |
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| JP4715428B2 (en) * | 2005-09-28 | 2011-07-06 | 株式会社大林組 | Condensation occurrence determination method and condensation occurrence determination system |
| JP2007320157A (en) * | 2006-05-31 | 2007-12-13 | Maruji:Kk | Method for processing packaging container, packaging container, and processing data preparing system for packaging container |
| US20140020821A1 (en) * | 2012-07-19 | 2014-01-23 | II Donald J. Wagner | Method and Device for Imparting an Image onto a Surface via Condensation |
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