JP6418976B2 - Multilayer laminate with amorphous fluororesin coating film formed on water repellent surface - Google Patents

Description

  The present invention relates to a multilayer laminate in which an amorphous fluororesin coating film is formed on the entire surface or part of the surface of a substrate having a water repellent surface. More specifically, the present invention relates to a multilayer laminate in which an amorphous fluororesin coating film is formed on the entire surface or part of the surface of a substrate having a water-repellent surface that is coated with a fluororesin.

  Appliances such as cooking appliances coated with a fluororesin have been widely used for many years because of their anti-adhesive properties. In such a device, the fluororesin coating layer is formed by applying one or more coatings on a metal substrate such as aluminum. The coating of two or more layers usually includes an undercoat (primer layer) of an undercoat that adheres to the substrate and an overcoat (topcoat layer) that imparts an adhesion preventing function.

  For equipment coated with fluororesin, for functional purposes, a label or marking on the fluororesin coating, for example, a water level scale on the inner surface of a rice cooker covered with fluororesin, or in other cases In some cases, it may be desirable to improve the appearance of these cooking utensils by applying a decorative pattern on the fluororesin coating. In order to meet such a demand, a method has been proposed in which a scale or the like is printed and displayed on the inner surface of a container coated with a fluororesin with a fluororesin having a color different from that of the coated fluororesin (Patent Documents 1 and 2). ). However, since the surface of the base material to be printed has water repellency, printing a scale display etc. using a fluororesin paint will cause the paint to repel, bleed and rise on the base material, resulting in clear text and images. Is difficult to obtain.

  As another method, a primer layer is applied on a substrate and dried, and a printed layer of ink in which a fluororesin and a pigment are dispersed is formed thereon by tampo printing, and then a top layer made of the fluororesin is formed. A method of forming a fluororesin laminate by applying and baking has been proposed (Patent Document 3). However, such a method can be performed when the base material is coated with a fluororesin, but the surface of the fluororesin-coated base material having water repellency obtained by baking the fluororesin can be arbitrarily labeled as necessary. Alternatively, it is impossible to add a marking or form a decorative pattern.

  A method of forming a label, marking or decorative pattern on an anti-adhesion surface coated with a fluororesin has also been proposed. For example, Patent Document 4 discloses an ink composition according to an invention relating to an ink composition, in which a pigment, an antifoaming agent, a viscosity modifier and the like are added to a fluororesin aqueous dispersion on an adhesion-preventing surface formed on a substrate. There has been proposed a method of drying by heating after printing. In this proposed method, the ink composition is a dispersion in which the fluororesin particles and the colorant (pigment) are dispersed in the ink composition, and a shearing force such as stirring, spraying or coating is applied. In this case, since the viscosity of the composition is lowered, it is necessary to increase the viscosity of the ink composition with a thixotropic agent, or to add an antifoaming agent, an antigelling agent, an antisettling agent, or the like. For this reason, adjustment of the composition for obtaining a viscosity suitable for the printing process and apparatus becomes complicated and difficult, and the physical properties are lowered, and depending on the processing method, the fluororesin fine particles and the colorant (pigment) are aggregated. There is a possibility of inviting.

JP-A-1-170428 JP-A-2-36815 Japanese Patent No. 2605964 Special table 2014-530259 gazette JP 2014-70100 A

The present inventors have proposed the formation of a thin film coating of amorphous fluororesin (Patent Document 5), but the contact angle is 90 degrees or more, such as the surface of a substrate coated with fluororesin. As a result of the development of a fluororesin solution that can be applied to the entire surface or a part of the surface of a substrate having a water-repellent surface to form a label, marking, or decorative pattern on the surface, the present invention has been achieved. It is a thing.
The present invention provides a multilayer laminate comprising a structure in which the whole or part of a substrate having a water repellent surface such as the surface of a substrate coated with a fluorine-containing resin is coated with a fluorine resin.
The present invention further provides a multilayer laminate in which a fluororesin coating film of a fluororesin solution is formed on the entire surface or a part of a substrate having a water-repellent surface such as the surface of a fluororesin-coated substrate. Provide a way to do it.

The present invention relates to a fluorine-containing resin coating having a contact angle of 90 degrees or more formed from a fluorine-containing resin having a heat of fusion calculated from any endotherm detected in differential scanning calorimetry (DSC) of 3 J / g or more. A character or graphic is drawn, comprising a substrate having a surface formed by the above and a coating layer of an amorphous fluororesin containing a colorant that forms a character or graphic partially formed on the surface A multilayer laminate is provided.

  The amorphous fluororesin has a heat of fusion of less than 3 J / g calculated from any endotherm detected in differential scanning calorimetry (DSC), and according to ASTM D1238, a load of 5 kg and a measurement temperature of 250 ° C. The multilayer laminate having a melt flow rate (MFR) measured at ± 0.1 of 0.1 to 100 g / 10 min is a preferred embodiment of the present invention.

  The amorphous fluororesin is a tetrafluoroethylene / perfluoro (ethyl vinyl ether) copolymer, tetrafluoroethylene / perfluorodimethyldioxole copolymer, tetrafluoroethylene / perfluoro (butenyl vinyl ether) copolymer The multilayer laminate, which is at least one selected from coalescence, is a preferred embodiment of the present invention.

  The multilayer laminate in which the amorphous fluororesin has a perfluoro (ethyl vinyl ether) content of 30 to 80% by weight based on the copolymer weight is a preferred embodiment of the present invention.

  The multilayer laminate in which the amorphous fluororesin coating film contains a filler is a preferred embodiment of the present invention.

  The multilayer laminate in which the surface having a contact angle of 90 degrees or more is a surface formed by coating with a fluorine-containing resin is a preferred embodiment of the present invention.

The heat of fusion calculated from any endotherm detected in the differential scanning calorimetry (DSC) of the resin used for the fluorine-containing resin coating is 3 J / g or more. The multilayer laminate is a preferred embodiment of the present invention.
The fluororesin includes polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), and ethylene / tetrafluoroethylene. the multi-layer stack is at least one selected copolymer (ETFE) or colleagues is a preferred embodiment of the present invention.

The present invention also provides that the heat of fusion calculated from any endotherm detected in differential scanning calorimetry (DSC) is 3 J / g on a part of the surface of a substrate having a surface with a contact angle of 90 degrees or more. An amorphous fluororesin having a melt flow rate (MFR) of 0.1 to 100 g / 10 min measured at a load of 5 kg and a measurement temperature of 250 ° C. ± 0.1 in accordance with ASTM D1238 is organic. Provided is a method for producing a multilayer laminate in which letters or figures to be heated to the boiling point or higher of the organic solvent after applying a solution dissolved in a solvent.

The present invention further provides that the heat of fusion calculated from any endotherm detected in differential scanning calorimetry (DSC) is 3 J / g on a part of the surface of the substrate having a surface with a contact angle of 90 degrees or more. An amorphous fluororesin having a melt flow rate (MFR) of 0.1 to 100 g / 10 min measured at a load of 5 kg and a measurement temperature of 250 ° C. ± 0.1 in accordance with ASTM D1238 is organic. After applying a solution dissolved in a solvent and heating to a temperature equal to or higher than the boiling point of the organic solvent, further forming a fluorine-containing resin coating on the surface and firing the letter at a temperature equal to or higher than the melting point of the fluorine-containing resin or Provided is a method for producing a multilayer laminate in which a figure is drawn .

  The above-mentioned method for producing a multilayer laminate in which the amorphous fluororesin has a perfluoro (ethyl vinyl ether) content of 30 to 80% by weight based on the copolymer weight is a preferred embodiment of the present invention.

According to the present invention, it is applied to a part of a substrate having a water repellent surface having a contact angle of 90 degrees or more, such as the surface of a substrate coated with a fluorine-containing resin, and a label, marking, Alternatively, an amorphous fluororesin solution capable of forming a decorative pattern and a multilayer laminate in which the amorphous fluororesin solution is applied on the surface of the equipment are provided.
Also the present invention, such as fluorine-containing resin coated substrate surface, the contact angle is applied to a portion of a substrate having a surface is also water-repellent than 90 degrees, a label to the surface, marking Alternatively, a method for producing a multilayer laminate in which an amorphous fluororesin solution capable of forming a decorative pattern is applied on the surface of an equipment is provided.
To provide a multilayer laminate in which a label, marking or decorative pattern is formed as a clear and sharp image on a substrate surface having a water-repellent surface with a contact angle of 90 degrees or more by the fluororesin solution of the present invention. it can.
Conventionally known water-based fluororesin paint has a contact angle of 90 degrees or more, and the surface of the substrate coated with a water-repellent fluororesin will cause the paint to repel, bleed, and rise. However, the fluororesin solution of the present invention made it possible to form a fluororesin coating film on which desired letters or figures were drawn .

FIG. 3 is a view showing a photograph of a printing pattern obtained in Example 1. FIG. 5 is a view showing a photograph of a printing pattern obtained in Example 2. FIG. 6 is a view showing a photograph of a print pattern obtained in Example 3. FIG. 6 is a view showing a photograph of a print pattern obtained in Example 4. FIG. 10 is a view showing a photograph of a printing pattern obtained in Example 5. 5 is a diagram showing a photograph of a printing pattern obtained in Comparative Example 1. FIG.

The present invention relates to a fluorine-containing resin coating having a contact angle of 90 degrees or more formed from a fluorine-containing resin having a heat of fusion calculated from any endotherm detected in differential scanning calorimetry (DSC) of 3 J / g or more. The present invention provides a multilayer laminate in which characters or figures including a base material having a surface formed by the above-described method and an amorphous fluororesin coating film layer formed on a part of the surface are drawn .
The present invention also provides a fluorine-containing resin having a contact angle of 90 ° or more formed from a fluorine-containing resin having a heat of fusion calculated from any endotherm detected in differential scanning calorimetry (DSC) of 3 J / g or more. There is also provided a method for producing a multilayer laminate in which letters or figures including a substrate having a surface formed by a film and an amorphous fluororesin coating layer formed on a part of the surface are drawn. Is.

Amorphous fluororesin The fluororesin of the present invention is an amorphous fluororesin. The amorphous fluororesin preferably has a heat of fusion calculated from any endotherm detected by differential scanning calorimetry (DSC) of the polymer of less than 3 J / g, preferably less than 1 J / g. Such an amorphous fluoropolymer generally does not show endotherm in the second DSC heating even if weak endotherm is detected in the first heating.

Examples of the amorphous fluororesin include a copolymer (PFA) containing tetrafluoroethylene (TFE) and perfluoro (alkyl vinyl ether) (PAVE), a tetrafluoroethylene / perfluorodimethyldioxole copolymer, Examples thereof include a tetrafluoroethylene / hexafluoropropylene copolymer and a tetrafluoroethylene / perfluoro (butenyl vinyl ether) copolymer.

Among these, a preferred example of the amorphous fluororesin includes a copolymer (TFE / PEVE copolymer) containing tetrafluoroethylene (TFE) and perfluoro (ethyl vinyl ether) (PEVE).
The content of PEVE in the TFE / PEVE copolymer is preferably 20 to 80% by weight, preferably 30 to 70% by weight, more preferably 40 to 60% by weight based on the weight of the copolymer.
Further, in accordance with ASTM D1238 of TFE / PEVE copolymer, the melt flow rate (MFR) measured at a load of 5 kg and a measurement temperature of 250 ° C. ± 0.1 is 0.1 to 100 g / 10 minutes, preferably 30 to 100 g. / 10 minutes, more preferably 50 to 100 g / 10 minutes by weight.

  The TFE / PEVE copolymer means a fluoropolymer containing TFE and PEVE as the main polymer units, and is preferably a TFE / PEVE binary copolymer, but also has other additional non-functionality or It may contain a functional fluorinated comonomer. Other additional non-functional fluorinated comonomers that may be included include, for example, 1 or 3 to 5 fluoroolefins (other than TFE) and alkyl groups having 2 to 8 carbon atoms. And fluorinated alkyl vinyl ethers containing the following carbon atoms. As preferred examples of such other additional non-functional fluorinated comonomers, the fluoroolefins include hexafluoropropylene (HFP) and chlorotrifluoroethylene (CTFE).

Comonomers which are fluorinated other additional functionality, e.g., perfluoro (methyl vinyl ether), _{or, CF 2 = CF-OCF 2} CF 2 -SO 2 F; CF 2 = CF [OCF 2 CF (CF _{3)] O (CF 2)} in 2 -Y (wherein, Y is -SO ₂ F or -CN); and _{CF 2 = CF [OCF 2 CF} (CF 3)] O (CF 2) 2 -CH (wherein, Z is -OH, -OCN, -O (CO) NH 2 or -OP (O) _(OH) a _{2) 2} -Z-functional fluorinated monomer selected from the group consisting of Is mentioned. Other additional fluorinated comonomers may be used alone or in combination of two or more.

The amorphous fluororesin according to the present invention can be appropriately selected from the market and used, but examples of the amorphous fluororesin that can be obtained from the market other than PFA include the following. .
(A) Teflon (registered trademark) AF1600 [trade name, manufactured by DuPont, tetrafluoroethylene / perfluorodimethyldioxole] copolymer, Tg = 160 ° C.],
(B) Teflon (registered trademark) AF2400 [trade name, manufactured by DuPont, tetrafluoroethylene / perfluorodimethyldioxole copolymer, Tg = 240 ° C.]
(C) Teflon (registered trademark) SF-60 [trade name, manufactured by DuPont, tetrafluoroethylene / perfluoromethyl vinyl ether / perfluoroethyl vinyl ether copolymer],
(D) Teflon (registered trademark) SF-50 [trade name, manufactured by DuPont, tetrafluoroethylene / hexafluoropropylene] copolymer],
(E) Cytop [trade name, manufactured by Asahi Glass Co., Ltd., tetrafluoroethylene / perfluoro (butenyl vinyl ether) copolymer]

Organic Solvent The organic solvent of the present invention may be any organic solvent that can dissolve the amorphous fluororesin, such as aliphatic hydrocarbons, alicyclic hydrocarbons, directional hydrocarbons, ethers, amines, etc. Can be appropriately selected and used.

  A preferred example of the organic solvent of the present invention is a fluorine-containing solvent. A particularly preferred fluorine-containing solvent is a solvent in which an atom bonded to carbon of an organic solvent is completely substituted with fluorine (hereinafter referred to as a complete fluorine-substituted solvent), or a solvent in which a part of atoms bonded to carbon is substituted with fluorine (hereinafter referred to as a fluorine-containing solvent). A partial fluorine-substituted solvent). Among these, a solvent in which at least 50% of all atoms bonded to carbon are fluorine atoms in such a complete fluorine-substituted solvent or a partially fluorine-substituted solvent is preferable.

  As described above, the perfluorinated solvent is a so-called perfluorinated compound in which all atoms bonded to carbon are fluorine atoms. The perfluorinated solvent is preferably at least one selected from perfluorocarbons, halogen-substituted ethers, sulfur-containing perfluoro compounds and nitrogen-containing perfluoro compounds. Specific examples of such a perfluorinated solvent include, for example, perfluorocyclobutane, perfluorodecalin, perfluoro (1-methyldecalin), perfluoro (dimethyldecalin), perfluoro (tetradecahydrophenanthrene), and perfluoro. Fluorinated cycloalkanes such as methylcyclohexane and perfluoro (cyclohexylmethyl) decalin; Fluorinated aromatic compounds such as perfluorobenzene, perfluoronaphthalene and perfluorobiphenyl; perfluoro (2-n-butyltetrahydrofuran) Perfluorinated compounds such as perfluoro-1,4-dithiane, perfluorothiepane, perfluorodiethylsulfone, perfluorooctanesulfonyl fluoride, and the like; Fluorinated alkylamines such as dimethylbutylamine); fluorinated trialkylamines such as perfluoro (triamylamine), perfluoro (tributylamine), perfluoro (tripentylamine), etc. it can.

  The boiling point of the perfluorinated solvent is preferably 50 ° C. or higher, more preferably 100 ° C. or higher. When the perfluorinated solvent is a fluorinated cycloalkane and a fluorinated aromatic compound, the boiling point is preferably 70 ° C. or higher, more preferably 140 ° C. or higher.

The partially fluorine-substituted solvent is preferably at least one selected from hydrofluorocarbons and partially halogen-substituted ethers. The partially fluorinated solvent is at least one selected from partially fluorinated solvents having up to about 12.5 atomic percent hydrogen and / or up to 37.5 atomic percent chlorine, based on all atoms bonded to carbon atoms. Preferably it is a seed. Specific examples of the partially fluorinated solvent include decafluoropentane represented by C ₅ H ₂ F ₁₀ (representative examples: 1,1,1,2,3,4,4,5,5,5). HFC alkane represented by the following formula (1) such as -decafluoropentane); HFC alkene represented by the following formula (2); perfluoro (propyl) methyl ether, perfluoro (butyl) methyl ether, perfluoro ( And perfluoro (alkyl) alkyl ethers such as hexyl) methyl ether and perfluoro (butyl) ethyl ether.
_{C n F 2n + 2-x} H x (n = 6~15, x = 1~3) (1)
_{C n F 2n-x H x} (n = 7~15, x = 1~3) (2)

  As the fluorine-substituted solvent of the present invention, the solvents disclosed in US Pat. No. 5,328,946 and US Pat. No. 5,397,829 can also be used.

Fluorine resin solution An amorphous fluororesin solution used in the present invention can be obtained by dissolving an amorphous fluororesin in a fluorine-substituted solvent. The concentration of the amorphous fluororesin in the amorphous fluororesin solution is preferably 0.01 to 10% by weight, and more preferably 0.5 to 5% by weight.
There is no restriction | limiting in particular in the method to melt | dissolve an amorphous fluororesin in an organic solvent, A conventionally well-known method is employable. When ultrasonic treatment is performed when the amorphous fluororesin is dissolved in an organic solvent, the dissolution can be promoted.

An additive can be added to the fluororesin solution of the present invention at a desired ratio as desired. When using the additive, the order of addition of the amorphous fluororesin, the organic solvent solution and the additive is not particularly limited.
Additives that can be used in the fluororesin solution can be appropriately selected depending on the purpose of addition. For example, when a desired color is developed in the fluororesin solution, a colorant may be selected from known ones and added. Examples of the colorant include organic pigments, inorganic pigments, and other colorants. Examples of inorganic pigments include titanium dioxide (titanium white), titanium yellow, aluminum iron titanate, iron oxide, carbon black, ultramarine, boron nitride (BN), etc., as well as titanium dioxide, iron oxide, etc. There are also mica coated with these pigments. Two or more of these may be mixed and used.
When using a colorant, it is used at 0.001 to 500 parts by weight, preferably 0.01 to 300 parts by weight, more preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the amorphous fluororesin. It is preferable to do.

  In addition, a filler can be added to affect physical properties such as surface hardness and surface shape of the fluororesin solution. A filler can also be suitably selected from well-known things according to the objective. Fillers include inorganic fillers such as metal oxides, glass particles, ceramic particles, metal particles, crystalline fluororesin, polyamideimide, polyimide, polyetherimide, polyethersulfone, polysulfone, polybenzimidazole, There are also organic fillers such as polyphenylene sulfide and polyether ether ketone. As the organic filler, a crystalline fluororesin can be preferably used. By adding a filler, it is possible to intentionally form an uneven surface on the fluororesin coating film, thereby improving design properties, water repellency, releasability and the like.

  The fluororesin solution of the present invention may further contain other additives as long as the object of the present invention is not impaired. Examples of other additives include various stabilizers, wetting agents, leveling agents, and dispersing agents.

  In the solution, since it is important to adjust the viscosity according to the situation of use, a thickening agent for adjusting the viscosity is used in a normal solution, but in the fluororesin solution of the present invention, the fluorine to be transferred is used. By appropriately selecting the type of resin and the concentration in the fluororesin solution, the target viscosity of the fluororesin solution can be easily obtained.

Substrate having water-repellent surface The water-repellent surface of the substrate having the water-repellent surface of the present invention is a surface having a contact angle of 90 degrees or more. As such a water-repellent surface, for example, a surface having water repellency which is coated with a fluorine-containing resin and has a contact angle of 90 degrees or more can be exemplified. Conventionally known water-based fluororesin paint has a contact angle of 90 degrees or more, and the surface of the substrate coated with a water-repellent fluororesin will cause the paint to repel, bleed, and rise. However, if the above-described fluororesin solution of the present invention is used, a desired fluororesin coating film can be formed.
A typical example of a substrate having a water repellent surface is a substrate having a fluorine-containing resin-coated surface having a contact angle of 90 degrees or more. This fluorine-containing resin coating is formed on the surface of a substrate such as aluminum, anodized aluminum, cold rolled steel, stainless steel, enamel, glass, or glass ceramic.

Such, the fluorine-containing resin used in the fluorine-containing resin coating to form a surface that exhibits a 90-degree or more water-repellent, even heat of fusion calculated from any endotherm detected in a differential scanning calorimetry (DSC) 3J / g or more fluorine-containing resin, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer ( FEP) and ethylene / tetrafluoroethylene copolymer (ETFE), etc. is.

  The base material having a surface with a contact angle of 90 degrees or more includes instruments, containers and other objects having such a water-repellent surface, and a typical example is an object coated with a fluororesin. Specific examples include cooking utensils such as frying pans, sauce pans, and rice cookers, but are not limited thereto.

Method for producing a fluororesin coating multilayer laminate A repellent having a fluororesin coating formed by applying the fluororesin solution of the present invention to the whole or part of the water repellent surface of a substrate having a water repellent surface. A substrate having an aqueous surface is obtained as the multilayer laminate of the present invention.
Manufacture of a multilayer laminate in which the fluororesin solution of the present invention is applied to the whole or a part of the water repellent surface of a substrate having a water repellent surface, and then heated to the boiling point of the organic solvent contained in the fluororesin solution. The method is a preferred embodiment of the present invention.
The fluororesin coating film formed on the water repellent surface is usually 0.1 to 3000 μm, preferably 0.1 to 2000 μm, and more preferably 0.1 to 1000 μm.

  In forming the multilayer laminate of the present invention, the fluororesin coating film is formed by applying the fluororesin solution of the present invention to the entire surface or a part of the water repellent surface of the substrate having a water repellent surface. Further, a multilayer laminate may be produced by forming a film of a fluororesin on the surface and firing at a temperature equal to or higher than the melting point of the fluororesin. Examples of such a fluorine-containing resin include those exemplified as the fluorine-containing resin forming the substrate having the water-repellent surface.

Also, the heat of fusion calculated from any endotherm detected by differential scanning calorimetry (DSC) is less than 3 J / g on the whole or part of the surface of the substrate having a surface with a contact angle of 90 degrees or more. In accordance with ASTM D1238, an amorphous fluororesin having a melt flow rate (MFR) of 0.1 to 100 g / 10 min measured at a load of 5 kg and a measurement temperature of 250 ° C. ± 0.1 is an organic solvent. A method for producing a multilayer laminate in which a solution dissolved in is heated to a temperature equal to or higher than the boiling point of the organic solvent is a preferred embodiment of the present invention.
In the present invention, after the multilayer laminate is formed in this manner, a coating of the fluorine-containing resin is further formed on the surface, and then the multilayer laminate is fired at a temperature equal to or higher than the melting point of the fluorine-containing resin. It can also be manufactured.

  When the water-repellent surface is a surface coated with a fluorine-containing resin, since both the fluorine-containing solvent constituting the fluororesin solution and the amorphous fluorine resin have affinity with the coated fluorine resin, The resulting fluororesin coating film exhibits good adhesion to the fluororesin coating, and has excellent thermal stability and wear resistance, as well as labels, markings and decorations drawn with the fluororesin coating film. The pattern gives a clear and sharp image.

  The labels, markings, decoration patterns and the like drawn with the fluororesin coating film are not particularly limited, and various patterns, characters, scales and the like can be mentioned. In terms of design, it is possible to form geometrical patterns, illustrations of people, landscapes, still life, etc., paintings, photographs, calligraphy, character designs, symbols such as emblems, corporate logos, messages, etc.

  The coating method for forming the fluororesin coating film using the fluororesin solution of the present invention is not particularly limited, but by spray coating, transfer, flow coating, screen coating and other printing methods, spin coating, roll coating, etc. Can be painted. Among these coating methods, spray coating is preferable because it is easy to obtain a fluororesin coating film that is free from defects in the fluororesin coating film and that can be easily smoothed. For labels and marking, a method known as a printing method such as pad printing can be employed.

The present invention is used for imparting aesthetic and / or functional effects such as letters and figures to the entire surface or part of the surface of a substrate having a water-repellent surface with a contact angle of 90 degrees or more. Can do. As a typical field to which the present invention is applied, it is possible to give a label, a marking, a decorative pattern, etc. on a cooking utensil, a heat-resistant dish or the like that is coated with a fluorine-containing resin.
The present invention can also be applied to the field of printing on parts such as electronic / electric parts, optical parts, precision machine parts, and automobile parts. Examples include printing on wiring boards such as printed wiring boards and ceramic wiring boards, optical fibers, solar cells, touch panels, film capacitors, liquid crystals, plasma displays, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using a preparation example, an Example, and a comparative example, this invention is not limited to these examples.

A. Material 1. Amorphous fluororesin (1) Amorphous PFA
Copolymer of tetrafluoroethylene / perfluoro (ethyl vinyl ether) (Teflon (registered trademark) PFA (Mitsui / DuPont Fluoro Chemical Co., Ltd., heat of fusion 0 J / g, ethyl vinyl ether content 50% by weight, MFR 60 g / 10 min)
(2) AF
Tetrafluoroethylene / perfluorodimethyldioxole copolymer (Teflon (registered trademark) AF1600, manufactured by DuPont, heat of fusion 0 J / g, MFR 10 g / 10 min)

2. Crystalline PFA
Teflon (registered trademark) PFA 334-JR aqueous dispersion (solid content 60 wt%, heat of fusion 35 J / g, MFR 15 g / 10 min, perfluoro (alkyl vinyl ether) content wt%, manufactured by Mitsui DuPont Fluorochemicals)

3. Fluorine-containing solvent (1) Perfluorotributylamine (Fluorinert (trade name) FC-43, manufactured by 3M)
(2) 1, 1, 1, 2, 2, 3, 4, 5, 5, 5-decafluoro-3-methoxy-4- (trifluoromethyl) -pentane (Novec (trade name) 7300, manufactured by 3M Company )

4). Colorant (1) Carbon black (Printex (trade name) F80, manufactured by Orion)
(2) Titanium oxide (Tai Pure (registered trademark) R-900, manufactured by DuPont)
(3) Mica (Colorstream (trade name) T10-01, manufactured by Merck & Co., Inc.)
(4) Mica (Iriodin 504 (trade name) iron oxide coated mica, manufactured by Merck & Co., Inc.)
5. Thickener hydroxypropyl methylcellulose (Metroze 65SH-50 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.)

5. Base material (1) Base material A
Shot blasting (pneumatic blaster (trade name), manufactured by Fuji Seisakusho, air pressure 3 kgf / cm ² ) using # 60 alumina (showa blaster (trade name), Showa Denko) on the surface of aluminum (JIS A1050) ), And then sprayed with a PFA aqueous dispersion (Teflon (registered trademark) PFA PJ-AL916, manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) using W-88-10E manufactured by Anest Iwata. Spray coating at a pressure of 3 kgf / cm ² ) and drying at 120 ° C. for 10 minutes to form a primer layer having a thickness of 7 to 9 μm. Then, a tetrafluoroethylene / perfluoro (propyl vinyl ether) copolymer (TFE / PPVE copolymer) (MFR: 15 g / 10 min, average particle size: 18 μm) is applied onto the primer layer by electrostatic powder coating. Then, baking was performed at 390 ° C. for 20 minutes to form a topcoat layer having a thickness of 50 μm. The obtained fluororesin-coated aluminum plate was used as the substrate A. The topcoat layer is colorless and transparent, but the coating layer on the aluminum plate appears black because the primer layer is black.
The contact angle of the fluororesin-coated surface of the substrate A was 122 degrees.

(2) Base material B
In the preparation of the substrate A, the TFE / PPVE copolymer used for the electrostatic powder coating on the primer layer is replaced with a filler-containing tetrafluoroethylene / perfluoro (ethyl vinyl ether) copolymer (TFE / PEVE copolymer). ) (MFR: 2 g / 10 min, average particle size: 20 μm, particle size range of 11-22 μm oxide glass containing 10% by weight with respect to the total weight) This was obtained as a base material B. The topcoat layer was opaque and the color was ivory.
The contact angle of the fluororesin-coated surface of the substrate B was 120 degrees.

(3) Base material C
In the preparation of the substrate A, the TFE / PPVE copolymer used for electrostatic powder coating on the primer layer was replaced with a filler-containing TFE / PEVE copolymer (MFR: 2 g / 10 min, average particle size: 20 μm, A fluorine-containing resin-coated aluminum plate was obtained in the same manner except that the graphite having an average particle diameter of 1 to 106 μm was changed to 0.9 wt% based on the total weight. The topcoat layer was opaque and the color was gray.
The contact angle of the fluororesin-coated surface of the substrate C was 120 degrees.

(4) Base material D
In the preparation of the substrate A, the TFE / PPVE copolymer used for electrostatic powder coating on the primer layer was replaced with a filler-containing TFE / PEVE copolymer (MFR: 2 g / 10 min, average particle size: 20 μm, A fluororesin-coated aluminum plate was obtained in the same manner except that the carbon black having an average particle size of 40 μm was changed to 3.0% by weight based on the total weight. The topcoat layer was opaque and the color was black.
The contact angle of the fluororesin-coated surface of the substrate D was 120 degrees.

(5) Substrate E
In the preparation of the substrate A, the TFE / PPVE copolymer used for electrostatic powder coating on the primer layer was replaced with a filler-containing TFE / PEVE copolymer (MFR: 2 g / 10 min, average particle size: 20 μm, A fluororesin-coated aluminum plate was obtained in the same manner except that the silicon carbide having an average particle diameter of 20 μm was changed to 5.0% by weight based on the total weight. The topcoat layer was translucent and the color was gray.
The contact angle of the surface of the base E with the fluorine-containing resin coating was 120 degrees.

(6) Substrate F
The surface of aluminum A1050 was subjected to shot blasting (pneumatic blaster (trade name), manufactured by Fuji Seisakusho, air pressure 3 kgf / cm 2) using # 60 alumina (showa blaster (trade name), manufactured by Showa Denko KK). Thereafter, an aqueous PFA dispersion (Teflon (registered trademark) PFA PJ-AL916, manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was applied by spray coating (W-88-10E, manufactured by Anest Iwata, air pressure 3 kgf / cm 2). And a primer layer having a film thickness of 7 to 9 μm was formed by drying at 120 ° C. for 10 minutes. Then, a PFA aqueous dispersion (Teflon (registered trademark) PFA EJ-CL700, manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) is spray-coated on the primer layer, followed by drying at 120 ° C. for 10 minutes, followed by 400 ° C. Was baked for 20 minutes to form a 50 μm topcoat layer. The obtained fluororesin-coated aluminum plate was used as the base material F. The topcoat layer was opaque and the color was black.
The contact angle of the surface of the substrate F coated with the fluorine-containing resin was 120 degrees.

(7) Substrate G
In the preparation of the base material F, titanium oxide having an average particle diameter of 0.5 μm (10% by weight with respect to the total weight of the aqueous dispersion) was added to EJ-CL700 and spray coating was performed on the primer layer in the same manner. A material-containing fluororesin-coated aluminum plate was obtained and used as a base material G. The topcoat layer was opaque and the color was white.
The contact angle of the fluororesin-coated surface of the substrate G was 120 degrees.
(8) Substrate H
In the preparation of the base material F, carbon black having a primary average particle diameter of 16 nm (6% by weight with respect to the total weight of the coating material) was added to EJ-CL700 and spray coating was performed on the primer layer. A fluororesin-coated aluminum plate was obtained and used as a base material H. The topcoat layer was opaque and the color was black.
The contact angle of the fluororesin-coated surface of the substrate H was 120 degrees.
(9) Substrate I
In the preparation of the substrate F, a filler was similarly added except that 1% by weight of mica having a particle size range of 5 to 40 μm was added to EJ-CL700 and spray-coated on the primer layer. A fluororesin-coated aluminum plate was obtained and used as a base material I. The topcoat layer was opaque and the color was black.
The contact angle of the surface of the substrate I with the fluorine-containing resin coating was 120 degrees.

(10) Base material J
Polyethylene terephthalate film (CP-Leaf (trade name) laminate pouch film, manufactured by Fuji Pla Co., Ltd.)
The contact angle of the surface of the substrate J coated with the fluorine-containing resin was 81 degrees.

B. Measurement of physical properties (1) Contact angle The contact angle of the surface of the test specimen was measured by DropMaster DM-701 (manufactured by Kyowa Interface Co., Ltd.) according to JIS K6894, using a test standard solution as pure water and a liquid appropriate method.

(2) Printability (A) The application state of the solution on the printing surface when printing was performed using a repellent solution was visually observed and judged according to the following criteria.
A: It was applied according to a predetermined pattern.
○: Although not perfect, it was applied almost according to a predetermined pattern.
X: A portion lacking in the applied pattern was recognized and not applied according to a predetermined pattern.

(B) Whether or not the printed pattern when the printing was performed using the chipping solution drawn a predetermined pattern was visually observed and judged according to the following criteria.
A: Printed according to a predetermined pattern.
○: Although not perfect, it was printed almost according to a predetermined pattern.
X: A portion lacking in the printed pattern was recognized and was not printed in a predetermined pattern.

(C) When printing was performed using a faint solution, whether or not the solution was applied to the entire printed pattern was visually observed and judged according to the following criteria.
A: The entire printed pattern was clearly recognized.
○: Almost all of the printed pattern was clearly recognized.
(Triangle | delta): The part which cannot be recognized clearly in the printed pattern was recognized.
X: The entire printed pattern could not be clearly recognized.

(Example 1)
Preparation of fluororesin solution After dissolving 12 parts by weight of amorphous fluororesin polymer in a mixed fluorine-containing solvent of 54 parts by weight of Novec 7300 and 29 parts by weight of fluorinate, 5 parts by weight of carbon black is added as a colorant and mixed. Thus, a fluororesin solution (hereinafter referred to as “paint coating 1”) was prepared.
Printing on the base material Using the prepared fluororesin solution on the fluororesin-coated surface of the substrate G, printing is performed by a pad transfer printing machine using a silicone rubber pad, and the repellency, chipping and faintness of the paint are printed. evaluated. The evaluation results are shown in Table 1.
A photograph of the print pattern obtained in this example is shown in FIG. 1, but the print pattern can be clearly recognized without being chipped or faint.

(Example 2)
In the preparation of the fluororesin solution in Example 1, the fluororesin solution was prepared in the same manner except that the amorphous fluororesin polymer fluorine-containing solvent and the colorant described in Table 1 were used in the proportions described in the table, The substrate was changed to A and the printability of the prepared fluororesin solution was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.
Example 2 A photograph of the resulting printed pattern is shown in FIG.

(Examples 3 to 5)
In the preparation of the fluororesin solution in Example 1, the fluororesin solution was prepared in the same manner except that the amorphous fluororesin polymer fluorine-containing solvent and the colorant described in Table 1 were used in the proportions described in the table, The substrate was G as in Example 1 and the printability of the prepared fluororesin solution was evaluated in the same manner as in Example 1 and the evaluation results are shown in Table 1.
The photograph of the printing pattern obtained in Examples 3-5 was shown in FIGS.

(Comparative Example 1)
12 parts by weight of the crystalline fluororesin aqueous dispersion (solid content 60% by weight) as a fluororesin, 65 parts by weight of pure water, 8 parts by weight of the thickener, and 5 parts by weight of carbon black as a colorant A solution (“paint ratio 1”) was obtained. Using the obtained solution, printability was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.
A photograph of the print pattern obtained in Comparative Example 1 is shown in FIG. 6, but the print pattern cannot be clearly recognized.

(Examples 6 to 10)
Using the fluororesin solution prepared in Example 1, printing was performed on the fluororesin-coated surfaces of the substrates B to F in the same manner as in Example 1 to evaluate printability. The evaluation results are shown in Table 2.

(Examples 11 and 12)
Using the fluororesin solution prepared in Example 1, printing was performed on the fluororesin-coated surfaces of the substrates H and I in the same manner as in Example 1 to evaluate printability. The evaluation results are shown in Table 2.

(Comparative Example 2)
Using the fluororesin solution prepared in Comparative Example 1 (“paint ratio 1”), printing was performed on the surface of the substrate J in the same manner as in Example 1 to evaluate printability. The evaluation results are shown in Table 3.

According to the present invention, it is applied to a part of a substrate having a water repellent surface having a contact angle of 90 degrees or more, such as the surface of a substrate coated with a fluorine-containing resin, and a label, marking, Alternatively, an amorphous fluororesin solution capable of forming a decorative pattern and a multilayer laminate in which the amorphous fluororesin solution is applied on the surface of the equipment are provided.
In the multilayer laminate provided by the present invention, a label, marking or decorative pattern can be formed as a clear and sharp image on a substrate surface having a water-repellent surface with a contact angle of 90 degrees or more.
Conventionally known water-based fluororesin paint has a contact angle of 90 degrees or more, and the surface of the substrate coated with a water-repellent fluororesin will cause the paint to repel, bleed, and rise. However, the fluororesin solution of the present invention made it possible to form a desired fluororesin coating film.
The present invention provides a substrate having a water-repellent surface with a contact angle of 90 ° or more, and imparts aesthetic and / or functional effects such as letters and figures to a part of the surface. The present invention can be applied to a field in which a label, a marking, or a decoration pattern is given to a cooking utensil using a cooking utensil or on a heat-resistant dish.
The present invention can also be applied to the field of printing on electronic / electrical parts, optical parts, precision machine parts, automobile parts, and other parts such as pellicle films in semiconductor manufacturing processes. Specifically, application to printing on wiring boards such as printed wiring boards and ceramic wiring boards, optical fibers, solar cells, touch panels, film capacitors, liquid crystals, plasma displays and the like is expected.

Claims (11)

The heat of fusion calculated from any endotherm detected in differential scanning calorimetry (DSC) was formed from a fluororesin film having a contact angle of 90 degrees or more formed from a fluororesin having a heat of fusion of 3 J / g or more. A multilayer laminate in which letters or figures are drawn, comprising a substrate having a surface and a coating layer of an amorphous fluororesin containing a colorant that forms letters or figures on a part of the surface.   The amorphous fluororesin has a heat of fusion of less than 3 J / g calculated from any endotherm detected in differential scanning calorimetry (DSC), and according to ASTM D1238, a load of 5 kg and a measurement temperature of 250 ° C. The multilayer laminate according to claim 1, wherein the melt flow rate (MFR) measured at ± 0.1 is 0.1 to 100 g / 10 min.   The amorphous fluororesin is a tetrafluoroethylene / perfluoro (ethyl vinyl ether) copolymer, tetrafluoroethylene / perfluorodimethyldioxole copolymer, tetrafluoroethylene / perfluoro (butenyl vinyl ether) copolymer The multilayer laminate according to claim 1 or 2, which is at least one selected from coalescence.   The multilayer laminate according to any one of claims 1 to 3, wherein the amorphous fluororesin has a content of perfluoro (ethyl vinyl ether) of 30 to 80% by weight based on the weight of the copolymer. The multilayer laminate according to any one of claims 1 to 4, wherein the amorphous fluororesin coating film further contains a filler. Resin used for the fluororesin coating is polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) and ethylene / tetrafluoroethylene copolymer (ETFE) or it selected at least one multilayer laminate according to claim 1. The heat of fusion calculated from any endotherm detected in differential scanning calorimetry (DSC) was formed from a fluororesin film having a contact angle of 90 degrees or more formed from a fluororesin having a heat of fusion of 3 J / g or more. A method for producing a multilayer laminate on which letters or figures are drawn, wherein a coating film of an amorphous fluororesin containing a colorant that draws letters or figures on a part of the surface is formed on the surface of a substrate having a surface . The heat of fusion calculated from any endotherm detected in differential scanning calorimetry (DSC) in the formation of the amorphous fluororesin coating film containing the colorant is less than 3 J / g, and conforms to ASTM D1238. A solution in which an amorphous fluororesin having a melt flow rate (MFR) of 0.1 to 100 g / 10 min measured at a load of 5 kg and a measurement temperature of 250 ° C. ± 0.1 is dissolved in an organic solvent and a colorant The manufacturing method of the multilayer laminated body of Claim 7 performed by apply | coating the mixture of this and heating it more than the boiling point of this organic solvent . The multilayer laminate according to claim 7 or 8, wherein after the amorphous fluororesin coating film is formed, a fluororesin coating film is further formed on the surface and then fired at a temperature equal to or higher than the melting point of the fluororesin. Body manufacturing method. The amorphous fluororesin is a tetrafluoroethylene / perfluoro (ethyl vinyl ether) copolymer, tetrafluoroethylene / perfluorodimethyldioxole copolymer, tetrafluoroethylene / perfluoro (butenyl vinyl ether) copolymer The method for producing a multilayer laminate according to any one of claims 7 to 9, which is at least one selected from coalescence. The amorphous fluororesin, wherein the copolymers of perfluoro 30-80 wt% tetrafluoroethylene / perfluoro content based on the co-polymer weight of (ethyl vinyl ether) (ethyl vinyl ether) 10. method for manufacturing a multilayer laminate according to.