TW202323212A - Method for producing layered object, method for producing base material, and base material - Google Patents

Abstract

The present invention provides a method for producing a layered object, a method for producing a base material, and a base material with which it is possible to form a protective film to which foreign substance derived from a base material is less likely to adhere in a production line and a transportation line. The present invention is a method for producing a layered object having a base material and a multi-tiered film, the method comprising a film formation step for forming the multi-tiered film by applying, to the base material, two or more types of aqueous solutions for protective film formation having different compositions.

Description

Method for producing laminate, method for producing substrate, and substrate

The present invention relates to a method for manufacturing a laminate, a method for manufacturing a base material, and the base material.

Substrates such as plate glass have been widely used for the surface layer or substrate of optical display devices, window glass, etc., especially in substrate applications such as optical display devices, it is necessary to remove stains or dust on the surface of the substrate, For example, pre-cleaning with a strong alkaline aqueous solution, etc., or performing a high-temperature treatment to burn off and wash the contaminated components on the surface, thereby achieving a clean state. On the other hand, for example, Patent Document 1 describes that polyvinyl alcohol having an average degree of polymerization of 600 or less and a degree of saponification of 40 mol% or more is used as a protective film for a glass substrate. In addition, Patent Document 2 describes a method of covering and protecting the surface of a glass substrate with a polyvinyl alcohol-based film. [Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Application Laid-Open No. 10-226537 Patent Document 2: Japanese Patent Laid-Open No. 2006-327881

[Problem to be Solved by the Invention]

However, as substrates such as glass for high-definition liquid crystals continue to become thinner, the management standards for foreign matter attached to the surface have become very strict. Especially in the production line and conveying line of the base material, foreign matters such as chips of the base material adhere to the surface of the base material to become a problem.

The object of the present invention is to provide a method for producing a laminate capable of forming a protective film, a method for producing a base material, and a base material. The above-mentioned protective film is less likely to adhere to foreign matter from the base material in production lines and conveying lines. [Technical means to solve the problem]

The present invention (1) relates to a method for producing a laminate having a base material and a multi-layer film. The method for producing the laminate includes a film forming step in which two or more kinds of Aqueous solutions are used to form protective films of different compositions to form multi-layered films. The present invention (2) is the method for producing a laminate according to the present invention (1), wherein at least one selected from the group consisting of adhesiveness, protection and peelability can be adjusted for the multilayer film. This invention (3) is the manufacturing method of the laminated body as described in this invention (1) or (2), which performs coating of the aqueous solution for protective film formation which has 2 or more different compositions continuously. The present invention (4) is the method for producing a laminate according to any one of the present inventions (1) to (3), wherein in the film forming step, the temperature of the substrate is 0°C to 400°C. The present invention (5) is a method for producing a laminate according to any one of the present inventions (1) to (4), including a base material forming step of forming a base material, and performing the base material forming step and film formation continuously step. This invention (6) is the manufacturing method of the laminated body as described in any one of this invention (1)-(5), wherein the aqueous solution for protective film formation of the 1st coating contains a plasticizer and water. The present invention (7) is the method for producing a laminate according to any one of the present inventions (1) to (6), wherein any of the plurality of protective film-forming aqueous solutions applied for the second time or thereafter is Those containing polyvinyl alcohol resin and water. The present invention (8) is the method for producing a laminate according to any one of the present inventions (1) to (7), wherein the aqueous solution for forming a protective film applied in the first coating does not contain a polyvinyl alcohol resin, or The polyvinyl alcohol resin content of the protective film-forming aqueous solution applied for the first time is less than the polyvinyl alcohol resin content of the protective film-forming aqueous solution applied for the second time or thereafter. The present invention (9) is a method for producing a laminate according to any one of the present inventions (1) to (8), wherein the aqueous solution for forming a protective film applied in the first application has a plasticizer content greater than that in the first application. The plasticizer content of the protective film-forming aqueous solution applied twice or later. The present invention (10) is a method for producing a laminate according to any one of the present inventions (1) to (9), wherein the plasticizer content of the aqueous solution for forming a protective film in the first coating is 0.1 to 80% by weight, and the water content is 20 to 99.9% by weight. The present invention (11) is the method for producing a laminate according to any one of the present inventions (1) to (10), wherein any of the aqueous solutions for protective film formation applied for the second time or thereafter The content of polyvinyl alcohol resin is 0.1-50% by weight, the content of plasticizer is 0.1-50% by weight, and the content of water is 10-99.8% by weight. The present invention (12) is a method for producing a substrate comprising the method for producing a laminate according to any one of the present inventions (1) to (11), and a removal step of removing the multilayer film from the substrate. This invention (13) is a base material obtained by the manufacturing method of the base material as described in this invention (12). The present invention (14) is an apparatus for performing the method for producing a laminate according to any one of the present inventions (1) to (11). The present invention (15) is an apparatus for performing the manufacturing method of the base material described in the present invention (12). The present invention will be described in detail below.

The inventors of the present invention have conducted intensive research and found that by coating aqueous solutions for forming a protective film having two or more different compositions to form a multi-layer film, it is possible to form a multi-layer film that is less likely to adhere to the substrate in a production line or a conveying line. The protective film of the foreign matter of the present invention has thus been completed.

The method for producing a laminate of the present invention includes a film forming step of coating a base material with two or more aqueous solutions for forming a protective film having different compositions to form a multilayer film. Thereby, at least one selected from the group consisting of adhesiveness, protectiveness, and peelability can be adjusted in the above-mentioned multilayer film.

In the above film forming step, it is preferable to continuously apply the protective film forming aqueous solution having two or more different compositions. In this case, it is possible to form a multi-layer film which can improve the adhesion between the films and which is also excellent in detachability from the base material. In addition, in the case of continuous coating, the method of applying the aqueous solution for protective film formation for the second application after applying the aqueous solution for forming a protective film for the first application; A method of applying the aqueous solution for protective film formation once, and then applying the aqueous solution for protective film formation two or more times. In addition, in this specification, any one of the aqueous solution for forming a protective film applied for the second time or the aqueous solution for forming a protective film applied thereafter is referred to as "multiple protective coatings applied for the second time or thereafter". Any of the aqueous solutions for film formation".

The aqueous solution for forming a protective film for the first coating preferably contains a plasticizer and water. The above-mentioned aqueous solution for forming a protective film for the first coating can increase the toughness of the protective film by containing a plasticizer. In addition, by containing the above-mentioned plasticizer, the solubility of the protective film in water can also be improved. Furthermore, the detachability of a protective film from a base material can also be improved by containing the said plasticizer.

It does not specifically limit as said plasticizer, For example, a polyhydric alcohol, a polyether, a phenol derivative, an amide compound etc. are mentioned. Moreover, the compound which added the ethylene oxide to a polyhydric alcohol is mentioned. These may be used alone or in combination of two or more.

Glycerin, diglycerin, diethylene glycol, trimethylolpropane, triethylene glycol, dipropylene glycol, propylene glycol etc. are mentioned as said polyhydric alcohol. Polyethylene glycol, polypropylene glycol, etc. are mentioned as said polyether. Bisphenol A, bisphenol S, etc. are mentioned as said phenol derivative. N-methylpyrrolidone etc. are mentioned as said amide compound. Among them, it is more preferable to use at least one selected from the group consisting of glycerin, diglycerin, diethylene glycol, trimethylolpropane, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol. , it is more preferable to use at least one kind selected from the group consisting of glycerol and diglycerol, and it is still more preferable to use diglycerol.

It is preferable that the aqueous solution for protective film formation of the said 1st coating has the said plasticizer content of 0.1-80 weight%. When the content of the above-mentioned plasticizer is within the above-mentioned range, the hydrophilicity of the surface of the base material can be controlled, the film can be formed uniformly, and the adhesive strength of the protective film to glass can be suppressed. The more preferable lower limit of the content of the above-mentioned plasticizer is 0.5% by weight, and the more preferable upper limit is 70% by weight. A more preferable lower limit is 1% by weight, and a more preferable upper limit is 60% by weight. A more preferable lower limit is 1.5% by weight, and a more preferable upper limit is 50% by weight. The lower limit is preferably 2% by weight, and the upper limit is preferably 40% by weight. A particularly preferable lower limit is 2.5% by weight, and a particularly preferable upper limit is 30% by weight.

Also, when the aqueous solution for forming a protective film for the first application contains a polyvinyl alcohol resin, it is preferable that the aqueous solution for forming a protective film for the first application contains more plasticizer than the aqueous solution for the second application. or the plasticizer content of any one of the aqueous solution for forming a protective film applied thereafter. It is more preferable that the plasticizer content of the aqueous solution for protective film formation of the said 1st application|coating is more than the plasticizer content of the aqueous solution for protective film formation of the 2nd or subsequent application|coating. The difference between the plasticizer content of the protective film-forming aqueous solution applied for the first time and the plasticizer content of the protective film-forming aqueous solution applied for the second time or thereafter is preferably 0.1 to 80% by weight. A more preferable lower limit is 0.5% by weight, and a more preferable upper limit is 70% by weight. A more preferable lower limit is 1% by weight, and a more preferable upper limit is 60% by weight. A more preferable lower limit is 1.5% by weight, and a more preferable upper limit is 50% by weight. The lower limit is preferably 2% by weight, and the upper limit is preferably 40% by weight. A particularly preferable lower limit is 2.5% by weight, and a particularly preferable upper limit is 30% by weight.

The aqueous solution for forming a protective film for the first coating contains 1 part by weight or more and 1000 parts by weight or less of the plasticizer relative to 100 parts by weight of the polyvinyl alcohol resin. When content of the said plasticizer is in the said range, the adhesive strength of a protective film to glass can be suppressed. The more preferable lower limit of the above-mentioned plasticizer content is 3 parts by weight, and the more preferable upper limit is 750 parts by weight. A more preferable lower limit is 5 parts by weight, and a more preferable upper limit is 500 parts by weight. A more preferable lower limit is 10 parts by weight, and a more preferable upper limit is 250 parts by weight. A more preferable lower limit is 15 parts by weight, and a more preferable upper limit is 100 parts by weight. A particularly preferable lower limit is 20 parts by weight, and a particularly preferable upper limit is 75 parts by weight.

The aqueous solution for forming a protective film for the first coating preferably contains water. It does not specifically limit as said water, For example, ion exchange water, pure water, etc. are mentioned. These may be used alone or in combination of two or more.

It is preferable that the aqueous solution for protective film formation of the said 1st coating has the said water content of 20 to 99.9 weight%. When the said water content exists in the said range, uniform film formation can be performed. A more preferable lower limit of the above-mentioned water content is 30% by weight, and a more preferable upper limit is 99.5% by weight. A more preferable lower limit is 40% by weight, and a more preferable upper limit is 99.0% by weight. A more preferable lower limit is 50% by weight, and a more preferable upper limit is 98.5% by weight. The lower limit is preferably 60% by weight, and the upper limit is preferably 98.0% by weight. A particularly preferable lower limit is 70% by weight, and a particularly preferable upper limit is 98.0% by weight.

The aqueous solution for forming a protective film for the first coating may contain water-soluble resins such as polyvinyl alcohol resins. In a good embodiment of the present invention, it is preferable that the aqueous solution for forming a protective film for the first application does not contain polyvinyl alcohol resin, or that the aqueous solution for forming a protective film for the first application contains a polyvinyl alcohol resin content. The polyvinyl alcohol resin content of the aqueous solution for forming a protective film that is less than the second or subsequent application. The above-mentioned aqueous solution for forming a protective film for the first application does not contain polyvinyl alcohol resin, or the aqueous solution for forming a protective film for the first application contains less polyvinyl alcohol resin than that for the second or subsequent application When the content of the polyvinyl alcohol resin in the aqueous solution for film formation is increased, the peelability of the protective film from the base layer can be further improved. By using the above-mentioned polyvinyl alcohol resin, the strength of the protective film can be increased. Also, soil biodegradability can be imparted.

The preferable lower limit of the degree of saponification of the polyvinyl alcohol resin is 50 mol%, and the preferable upper limit is 99.5 mol%. By setting it as the said range, a uniform aqueous solution can be produced, and the aqueous solution which can form a film can be produced. A more preferable lower limit of the degree of saponification is 60 mol %, a more preferable lower limit is 70 mol %, and an especially preferable lower limit is 80 mol %. A better upper limit is 99 mol%. Further, a preferable upper limit is 95 mol%. Preferably, the upper limit is 90 mole%. From the standpoint of aqueous solution formation and storage stability of an aqueous solution at room temperature, the polyvinyl alcohol resin is preferably a saponified product with a saponification degree of 98 mole % or less, particularly preferably a partially saponified product with a saponification degree of 90 mole % or less products, rather than more than 98 mole%. In addition, the said saponification degree is measured based on JISK6726. The degree of saponification represents the average value of the ratio of units actually saponified into vinyl alcohol units among units converted into vinyl alcohol units by saponification.

The degree of polymerization of the above-mentioned polyvinyl alcohol resin is not particularly limited, the lower limit is preferably 100, and the upper limit is 2500. A better lower limit is 200, and a better upper limit is 1800. Further, the lower limit is preferably 250, the upper limit is more preferably 1300, the lower limit is more preferably 300, and the upper limit is more preferably 1000. If it is within the above-mentioned range, both film strength and film-forming properties can be achieved at a relatively high level. In addition, the said degree of polymerization is measured based on JISK6726. In addition, from the viewpoint of film removability (peelability), polyvinyl alcohol resins with a high degree of polymerization are preferred, and polyvinyl alcohol resins with a relatively high degree of polymerization are preferred from the viewpoint of film production processes (especially spray processing). Low polyvinyl alcohol resin, because it can increase the concentration of aqueous solution. In consideration of the film removability, the most preferable range of the degree of polymerization is 200 to 800.

The above-mentioned polyvinyl alcohol resin may be a mixture of two or more resins with different degrees of saponification and polymerization, or a mixture of modified and unmodified resins.

The above-mentioned polyvinyl alcohol resin is obtained by polymerizing vinyl ester according to a conventionally known method to obtain a polymer, and then saponifying, ie, hydrolyzing, the polymer. Generally, alkali or acid can be used for saponification. For saponification, it is preferable to use an alkali. As said polyvinyl alcohol, only 1 type may be used, and 2 or more types may be used together.

Examples of the above-mentioned vinyl esters include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, vinyl versatate, vinyl laurate, and stearic acid. Vinyl esters and vinyl benzoate, etc. The polymer obtained by polymerizing the above-mentioned vinyl ester is preferably polyvinyl ester because it is easy to control the degree of saponification in a good range.

The polymerization method of the above-mentioned vinyl ester is not particularly limited. As this polymerization method, a solution polymerization method, a block polymerization method, a suspension polymerization method, etc. are mentioned.

As a polymerization catalyst used when the above-mentioned vinyl ester is polymerized, for example, 2-ethylhexyl peroxydicarbonate ("TrigonoxEHP" manufactured by Tianjin McEIT Co.), 2,2'-azobisisobutyronitrile ( AIBN), tert-butyl peroxyneodecanoate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, di-n-propyl peroxydicarbonate, di-n-butyl peroxydicarbonate, peroxide Dicetyl dicarbonate and di-butyl peroxydicarbonate, etc. The said polymerization catalyst may use only 1 type, and may use 2 or more types together.

Modified polyvinyl alcohol resin may also be contained in the said polyvinyl alcohol resin. The above-mentioned modified polyvinyl alcohol resin may be a copolymer of the above-mentioned vinyl ester and other monomers, or may be obtained by modifying a polyvinyl alcohol resin. Examples of the above-mentioned modified polyvinyl alcohol resins include acetoacetyl-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol, and nitrile-modified polyvinyl alcohol. Vinyl alcohol, amide modified polyvinyl alcohol, pyrrolidone modified polyvinyl alcohol or modified polyvinyl alcohol containing silicon atoms, or polyvinyl alcohol and (acrylamide, vinylpyrrolidone, acrylonitrile) Graft polymers of copolymers, etc.

Examples of the above-mentioned other monomers, that is, comonomers to be copolymerized, include olefins, (meth)acrylic acid and its salts, (meth)acrylates, (meth)acrylamide derivatives, N-ethylene Amides, vinyl ethers, nitriles, vinyl halides, allyl compounds, maleic acid and its salts, maleic acid esters, itaconic acid and its salts, itaconic acid esters, Vinyl silicon-based compounds, polyvinylpyrrolidone, and isopropenyl acetate, etc. The said other monomer may use only 1 type, and may use 2 or more types together.

As said olefins, ethylene, propylene, 1-butene, isobutene, etc. are mentioned. Examples of the (meth)acrylates include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate ) n-butyl acrylate, and 2-ethylhexyl (meth)acrylate, etc. Examples of the (meth)acrylamide derivatives include: acrylamide, n-methacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, and (methyl) Acrylamidopropanesulfonic acid and its salts, etc. N-vinylpyrrolidone etc. are mentioned as said N-vinyl amides. As said vinyl ethers, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, etc. are mentioned. (meth)acrylonitrile etc. are mentioned as said nitrile. Vinyl chloride, vinylidene chloride, etc. are mentioned as said vinyl halides. Allyl acetate, allyl chloride, etc. are mentioned as said allyl compound. Vinyltrimethoxysilane etc. are mentioned as said vinylsilyl compound.

A preferable upper limit of the modified amount (ratio of modified constituent units) in the above-mentioned modified polyvinyl alcohol resin is 25 mol%, and a more preferable upper limit is 20 mol%. Further, a preferable upper limit is 15 mol%. Also, the lower limit of the modified mass is preferably 2 mol%. By setting it as the said range, film physical property and water solubility can be made compatible at a high level.

When the above-mentioned aqueous solution for forming a protective film for the first coating contains a polyvinyl alcohol resin, the content of the polyvinyl alcohol resin is preferably 0.1 to 30% by weight. By setting the above-mentioned content to 0.1% by weight or more, a film with a high coverage rate can be formed (because when the substrate is at a high temperature, water vaporization will occur, so it can prevent the coated aqueous solution from breaking and making it difficult to case of film formation). Also, by setting it below 30% by weight, uniform film formation can be performed (if the concentration is too high, especially those with a high degree of saponification, gelation will partially occur at room temperature, and uniform coating cannot be achieved. ). A more preferable lower limit of the above content is 1% by weight, and a more preferable upper limit is 20% by weight. A more preferable lower limit is 2% by weight, and a more preferable upper limit is 15% by weight. Also, the polyvinyl alcohol resin content of the aqueous solution for forming a protective film applied for the first time is preferably less than the content of polyvinyl alcohol resin in the aqueous solution for forming a protective film applied for the second time or later, or the content of the polyvinyl alcohol resin in the aqueous solution for forming a protective film applied for the second time or later. The polyvinyl alcohol resin content of any of the aqueous solutions for protective film formation applied twice or thereafter. In this case, the adhesion, protection, and peelability of the film can be further improved. The difference between the content of polyvinyl alcohol resin in the aqueous solution for forming a protective film applied for the second time or thereafter and the content of polyvinyl alcohol resin in the aqueous solution for forming a protective film applied in the first time is preferably 0.1 to 50% by weight .

Various well-known additives may be blended in the aqueous solution for forming a protective film for the first coating as long as they do not interfere with the effects of the present invention. Examples of the additives include surfactants, antioxidants, antiaging agents, ultraviolet absorbers, titanium coupling agents, leveling agents, thixotropy imparting agents, anti-skinning agents, thickeners, thinners, and reactive thinners. , crosslinking agent, filler, pigment (pigment, dye), preservative, antifungal agent, etc. The aqueous solution for forming a protective film for the first coating preferably further contains an antifungal agent. Furthermore, as the above-mentioned antifungal agents, alcohol-based antifungal agents, aldehyde-based anti-fungal agents, thiazoline-based anti-fungal agents, imidazole-based anti-fungal agents, ester-based anti-fungal agents, chlorine-based anti-mold Oxide-based antifungal agents, carboxylic acid-based anti-fungal agents, urethane-based anti-fungal agents, sulfonamide-based anti-fungal agents, quaternary ammonium salt-based anti-fungal agents, pyridine-based anti-fungal Mold agent, iodine antifungal agent, triazole antifungal agent, etc.

Regarding the aqueous solution for forming the protective film for the first coating, it is preferable that the viscosity measured by a rotary viscometer (for example: TVC-10, manufactured by Toki Sangyo Co., Ltd.) is not less than 0.1 mPa・s and not more than 1 Pa・s . If it is in the said range, a uniform film can be formed. A more preferable lower limit of the above viscosity is 0.5 mPa·s, and a more preferable upper limit is 0.5 Pa·s. Further, a more preferable lower limit is 1 mPa·s, and a more preferable upper limit is 0.4 Pa·s. Furthermore, a more preferable lower limit is 1.5 mPa·s, and a more preferable upper limit is 0.3 Pa·s. Furthermore, the above viscosity is measured at 23°C.

It is preferable that the aqueous solution for forming a protective film for the first coating has a contact angle with a glass substrate (manufactured by SCHOTT, TEMPAX Float) at a temperature of 23°C and a humidity of 60% R/H of 20° to 70°. If it is in the said range, it will become easy to form a homogeneous film on a glass substrate. A more preferable lower limit of the above-mentioned contact angle is 25°, and a more preferable upper limit is 60°. A more preferable lower limit is 30°, and a more preferable upper limit is 50°. In addition, the said contact angle can be measured using a contact angle meter. As an example, the contact angle meter is DMo-502 (manufactured by Kyowa Interface Science Co., Ltd., analysis software FAMAS), the contact angle measurement substrate is glass (TEMPAX) 0.5 mm, and the measurement method is θ/2 method (A half- angle Method).

When the aqueous solution for forming a protective film is applied to the substrate, the temperature of the aqueous solution for forming a protective film is preferably at least 0°C, more preferably at least 10°C, further preferably at least 20°C, even more preferably at least 40°C, especially Preferably it is 60°C or higher, more preferably 100°C or lower, more preferably 95°C or lower, further preferably 90°C or lower, still more preferably 85°C or lower, especially preferably 80°C or lower. When the temperature of the aqueous solution for forming a protective film is within the above range, the protective film can be formed uniformly and rapidly, and workability is improved.

The method of producing the aqueous solution for forming a protective film for the first coating is not particularly limited, and examples thereof include a method of mixing a polyvinyl alcohol resin with a known method in addition to a plasticizer and water as necessary.

，cap HN400A）、T-AGPV（Devilbiss公司製造，口徑1.1 mm

，cap 805）等。又，作為上述塗料供給機器，可使用壓送泵PT-10DW（ANEST IWATA公司製造）等。 於進行上述利用噴霧之塗佈之情形時，較佳為將液壓設為0.7 MPa以下，將氣壓設為0.6 MPa以下，將壓送泵壓設為0.34 MPa以下。關於塗裝速度，較佳為設為1～100 mm/秒。 進而，作為使用AGB50作為上述噴槍之情形時之條件，可藉由將液壓設為0.6 MPa以下、將氣壓設為0.6 MPa以下、將壓送泵壓（液壓）設為0.34 MPa以下而良好地進行噴霧塗佈。 又，於使用T-AGPV作為上述噴槍之情形時，可藉由將液壓設為0.7 MPa以下、將霧化氣壓設為0.1～0.4 MPa、將氣壓設為0.35～0.5 MPa而良好地進行噴霧塗佈。 In the step of applying the aqueous solution for forming the protective film of the first coating on the above-mentioned base material, examples of the coating method include roll coating, dip coating, spin coating, spray coating, and spray coating. coating etc. Among them, coating by spraying is preferable from the viewpoint of coating efficiency and uniformity of the film. In the case of the above-mentioned spray coating (spray coating), depending on the pressure feeding system such as the paint feeder, or the type and condition of the spray gun, it can be properly coated within the specifications of the equipment used. . The type of the above-mentioned pressure feeding system or spray gun is preferably selected according to the viscosity of the aqueous solution. By selecting the type of pressure feeding system or spray gun according to the viscosity of the aqueous solution, atomization of the aqueous solution for forming a protective film or film formation by spraying can be easily performed. When the viscosity of the aqueous solution is high, it is necessary to choose a pressure delivery system that can set the hydraulic pressure to a higher level and a high-pressure spray gun that can handle high-viscosity liquids. In addition, in order to obtain the required discharge amount, it is also preferable to appropriately select the diameter of the nozzle cap. By increasing the diameter of the above-mentioned nozzle cap, the discharge amount can also be increased. However, when the pressure-feeding system of the aqueous solution for protective film formation or the corresponding pressure of the spray gun is insufficient, even if the diameter of the nozzle cap is increased, atomization cannot be performed, and good spray film formation cannot be performed. As the spray gun, for example, AGB50 (manufactured by Asahi Sunac, caliber 1.0 mm

, cap HN400A), T-AGPV (manufactured by Devilbiss, diameter 1.1 mm

, cap 805) etc. Moreover, as said paint supply apparatus, the pressure pump PT-10DW (made by ANEST IWATA company) etc. can be used. When performing the above-mentioned coating by spraying, it is preferable to set the hydraulic pressure at 0.7 MPa or less, the air pressure at 0.6 MPa or less, and the pressure pump pressure at 0.34 MPa or less. About coating speed, it is preferable to set it as 1-100 mm/sec. Furthermore, as the conditions when using AGB50 as the above-mentioned spray gun, it can be performed well by setting the hydraulic pressure to 0.6 MPa or less, the air pressure to 0.6 MPa or less, and the pressure pump pressure (hydraulic pressure) to 0.34 MPa or less. Spray application. Also, when T-AGPV is used as the above-mentioned spray gun, spraying can be carried out well by setting the hydraulic pressure at 0.7 MPa or less, atomizing air pressure at 0.1-0.4 MPa, and air pressure at 0.35-0.5 MPa cloth.

In the film forming step, the temperature of the base material when the aqueous solution for forming a protective film applied in the first application is preferably at least 0°C and not more than 400°C. When it is in the said range, if it applies to a high temperature board|substrate, a foam layer can be produced, and if it is low temperature, it can heat-dry after application|coating, and can produce a foam. The lower limit of the above temperature is preferably 15°C, the upper limit is 380°C, the lower limit is 40°C, the upper limit is 360°C, the lower limit is 75°C, and the upper limit is 340°C, especially A preferable lower limit is 100°C, a particularly preferable upper limit is 320°C, an especially more preferable lower limit is 150°C, and an especially more preferable upper limit is 300°C. When the temperature of the base material is 400°C or lower, it is possible to suppress foreign matter such as cutting chips from adhering to the surface of the substrate due to foam breaking, and the film and the base material are moderately bonded and easy to remove. If the base material temperature is 0° C. or higher, even if post-heating is performed, a foam can be easily formed.

As a method of adjusting the temperature of the above-mentioned base material, for example, when glass is formed by a melting method, a method of coating in a step of gradually cooling molten glass can be mentioned. Moreover, when using the glass after hardening, the method of heating glass is mentioned. The above-mentioned temperature means the temperature of the substrate surface at the time of coating. In addition, in the above-mentioned film forming step, the state of the substrate is not particularly limited, and for example, not only the state before the glass is molded and solidified, but also the state after the glass is solidified is also included. In addition, the above-mentioned base material may be polished or surface-treated as needed.

The preferable lower limit of the thickness when the above-mentioned aqueous solution for forming a protective film of the first coating is applied is 0.1 μm, and the preferable upper limit is 100 μm. If the thickness of the foam is within the above range, the foam layer can be peeled off and water-soluble. A more preferable lower limit of the thickness when the above-mentioned aqueous solution for forming a protective film in the first coating is applied is 1 μm, and a more preferable upper limit thereof is 80 μm. Further, the lower limit is preferably 1.5 μm, the upper limit is 60 μm, the lower limit is 2.0 μm, the upper limit is 40 μm, the lower limit is 2.5 μm, the upper limit is 30 μm, and the upper limit is 30 μm. A preferable lower limit is 3 μm, and a particularly preferable upper limit is 25 μm.

In the above-mentioned film forming step, it is preferable to use the following method: after applying the aqueous solution for protective film formation of the first application, the method of applying the aqueous solution for protective film formation of the second application; The method of applying the aqueous solution for forming a protective film multiple times after applying the aqueous solution for forming a protective film twice or more. After applying the above-mentioned aqueous solution for forming a protective film for the first application, further apply a plurality of aqueous solutions for forming a protective film for the second or subsequent application, thereby further improving the laminated body with the protective film. In the case of the substrate, the anti-adhesion property can also improve the peelability.

It is preferable that any one of the plurality of aqueous solutions for forming a protective film to be applied for the second time or thereafter contains a polyvinyl alcohol resin, a plasticizer, and water. As the polyvinyl alcohol resin, plasticizer, and water constituting any one of the plurality of protective film-forming aqueous solutions for the second or subsequent application, the same as the protective film-forming aqueous solution for the first application above can be used. the same.

The content of the polyvinyl alcohol resin in any of the plurality of protective film-forming aqueous solutions applied for the second time or thereafter is preferably 0.1 to 50% by weight. By making the above-mentioned content 0.1 weight% or more, the film with a high coverage can be formed, and by making it 50 weight% or less, uniform coating can be performed and a uniform film can be formed. A more preferable lower limit of the above content is 1% by weight, and a more preferable upper limit is 40% by weight. Furthermore, the lower limit is preferably 3% by weight, the upper limit is preferably 35% by weight, the lower limit is 5% by weight, the upper limit is 30% by weight, the lower limit is 8% by weight, and the upper limit is 8% by weight. 25% by weight.

In any of the plurality of protective film-forming aqueous solutions to be applied for the second time or thereafter, it is preferable that the plasticizer content is 0.1 to 50% by weight. When the said plasticizer content exists in the said range, the hydrophilicity of a glass surface can be controlled, and film formation can be performed uniformly. The more preferable lower limit of the above plasticizer content is 0.5% by weight, and the more preferable upper limit is 40% by weight. A more preferable lower limit is 1.0% by weight, and a more preferable upper limit is 30% by weight. A more preferable lower limit is 1.5% by weight, and a more preferable upper limit is 25.0% by weight. A preferable lower limit is 3.0% by weight, and a preferable upper limit is 20.0% by weight. A particularly preferable lower limit is 5.0% by weight, and a particularly preferable upper limit is 15.0% by weight.

It is preferable that any one of the plurality of protective film-forming aqueous solutions to be applied for the second time or thereafter contains 0.25 to 50,000 parts by weight of the plasticizer relative to 100 parts by weight of the polyvinyl alcohol resin. When content of the said plasticizer exists in the said range, toughness can be provided to a film. The more preferable lower limit of the above plasticizer content is 1.25 parts by weight, and the more preferable upper limit is 40000 parts by weight. A more preferable lower limit is 2.5 parts by weight, and a more preferable upper limit is 30000 parts by weight. A more preferable lower limit is 3.75 parts by weight, and a more preferable upper limit is 25000 parts by weight. A more preferable lower limit is 7.5 parts by weight, and a more preferable upper limit is 20000 parts by weight. A particularly preferable lower limit is 12.5 parts by weight, and a particularly preferable upper limit is 15000 parts by weight.

In any one of the plurality of protective film-forming aqueous solutions to be applied for the second time or thereafter, the water content is preferably 10 to 99.8% by weight. If the above-mentioned water content is within the above-mentioned range, it can be evenly coated on the surface of the substrate to produce a homogeneous film. If the concentration of water in the aqueous solution is too low, stringing problems may occur during spray formation. A more preferable lower limit of the above-mentioned water content is 20% by weight, and a more preferable upper limit is 99.0% by weight. A more preferable lower limit is 30% by weight, and a more preferable upper limit is 97.0% by weight. A more preferable lower limit is 40% by weight, a more preferable upper limit is 95.0% by weight, a more preferable lower limit is 42.5% by weight, a more preferable upper limit is 92.5% by weight, a more preferable lower limit is 45.0% by weight, and a more preferable upper limit is 90.0% by weight. In addition, the total content of the respective components contained in the aqueous solution for forming a protective film applied for the first time and the aqueous solutions for forming a protective film applied for the second time or later is 100% by weight.

Any one of the plurality of protective film-forming aqueous solutions to be applied for the second time or thereafter is preferably 0.1 mPa・s or more and 3.0 Pa・s or less. If it is within the above range, a uniform film with a high coverage can be formed. A more preferable lower limit of the above viscosity is 0.5 mPa·s, and a more preferable upper limit is 1.8 Pa·s. A more preferable lower limit is 1.0 mPa·s, and a more preferable upper limit is 1.0 Pa·s. A more preferable lower limit is 1.5 mPa·s, and a more preferable upper limit is 0.7 Pa·s. A more preferable lower limit is 50.0 mPa·s, and a more preferable upper limit is 0.5 Pa·s. Furthermore, the above viscosity is measured at 23°C.

Any one of the plurality of protective film-forming aqueous solutions that are applied for the second time or thereafter is preferably the contact angle with a glass substrate (eg, TEMPAX Float manufactured by SCHOTT) at a temperature of 23°C and a humidity of 60%RH It is not less than 10° and not more than 75°. If it is in the said range, it will become easy to form a homogeneous film on a glass substrate. A more preferable lower limit of the above-mentioned contact angle is 20°, and a more preferable upper limit is 70°. A more preferable lower limit is 25°, a more preferable upper limit is 65°, a more preferable lower limit is 30°, and a more preferable upper limit is 60°. In addition, the said contact angle can be measured using a contact angle meter. As an example, the contact angle meter is DMo-502 (manufactured by Kyowa Interface Science Co., Ltd., analysis software FAMAS), the contact angle measurement substrate is glass (TEMPAX) 0.5 mm, and the measurement method is θ/2 method (A half-angle Method ).

There are no particular limitations on the method of producing the plurality of protective film-forming aqueous solutions to be applied for the second time or thereafter, and examples thereof include a method of mixing polyvinyl alcohol resin, a plasticizer, and water by a known method.

As the step of applying the plurality of protective film-forming aqueous solutions for the second or subsequent application, the same method as the method for applying the protective film-forming aqueous solution for the first application above can be used. The step of applying the above-mentioned plurality of protective film-forming aqueous solutions applied for the second time or thereafter may be performed on only one side of the substrate, or may be performed on both sides.

A drying step (secondary drying) may also be performed after performing the above-mentioned film forming step. Thereby, a multilayer film can be formed regardless of the temperature of the base material. The drying temperature in the above-mentioned secondary drying is preferably not less than 50°C and not more than 450°C.

The method for producing the laminate of the present invention preferably includes a substrate forming step of forming a substrate, and the substrate forming step and the film forming step are performed continuously. In this case, foreign matters can be suppressed from adhering to the surface of the substrate or causing damage to the surface of the substrate. Examples of the substrate include glass, plastic substrates (organic polymer substrates), metal substrates, and the like. Examples of the glass include soda lime glass, alkali-free glass, borosilicate glass, fused silica, and the like. The present invention can be used particularly favorably for thin glass for high-definition liquid crystals. As said plastic base material, a polycarbonate board, a poly(meth)acrylic resin board, etc. are mentioned. As said poly(meth)acrylic-type resin board, a polymethyl(meth)acrylate board etc. are mentioned. Examples of the aforementioned metal substrates include substrates made of metals such as copper, iron, tin, aluminum, silver, stainless steel, brass, nickel, titanium, and alloys thereof. Specifically, a steel plate, a copper plate, an aluminum plate, an aluminum-plated steel plate, etc. are mentioned.

As the above-mentioned base material forming step, a known method can be used. When the above-mentioned base material is glass, as a method of forming glass, an orifice downdraw method, a fusion method, a float method, etc. are mentioned. Among them, it is preferable to use the melting method. The above-mentioned so-called melting method refers to directing the molten glass raw material to the slender gutter-shaped spout, overflowing on both sides along its length direction, and flowing downward, so that the flowing molten glass is reunited under the gutter, and In this state, it is slowly cooled and solidified while falling, thereby making glass. Furthermore, in the present invention, when using commercially available substrates such as glass, plastic substrates, and metal substrates, the step of shaping the above substrates is also performed.

According to the method for producing a laminate of the present invention, a laminate having a base material and a single-layer film or a base material and a multi-layer film can be obtained. In addition, for example, by continuous spray film forming method or continuous coating method, there are cases where spray coating is performed continuously before the drying step, and there is also a case where a film in which the interface between layers is integrated is produced. Therefore, the "multilayer film" in the present invention also includes those in which the interface between the layers is not clear and cannot be separated due to having a continuous gradient structure, etc., although the composition of the film is different.

The above-mentioned multilayer film preferably has a surface roughness Sa (arithmetic mean height described in ISO 25178) of 0.1 μm or more on the main surface opposite to the substrate. The upper limit is not particularly limited, and 30 μm is a substantial upper limit. Self-adhesive force can be reduced as it is the said range. The above-mentioned surface roughness Sa is preferably at least 0.2 μm, more preferably at least 0.3 μm, still more preferably at least 0.4 μm, particularly preferably at least 0.5 μm. In addition, the multilayer film to be formed in the present invention preferably has a surface roughness Sz (maximum height described in ISO 25178) of 10 μm or more on the main surface opposite to the substrate. The upper limit is not particularly limited, and 300 μm is a substantial upper limit. If it is in the said range, a base material can be protected from the surface scratches applied to a base material, or the damage by the pressure applied to a base material. The above-mentioned surface roughness Sz is preferably at least 20 μm, more preferably at least 30 μm, further preferably at least 40 μm, particularly preferably at least 50 μm. In addition, the above-mentioned multilayer film preferably has a surface roughness Sdr (maximum height described in ISO 25178) of 0.1 or more on the main surface opposite to the substrate. The upper limit is not particularly limited, and 30 is a substantial upper limit. If it is within the above range, the base material can be protected from damage caused by surface scratches applied to the base material or pressure applied to the base material, or the heat insulation of the base material can be improved. The above-mentioned surface roughness Sdr is more preferably 0.2 or more, still more preferably 0.3 or more, still more preferably 0.5 or more, particularly preferably 0.7 or more, especially preferably 0.9 or more. Furthermore, the above-mentioned surface roughness Sa, Sz and Sdr are measured on the main surface of the produced multilayer film by using a laser microscope (for example: morphology analysis laser microscope, VK-X1050, manufactured by Keynes Corporation) 1 mm×1 mm The range is calculated according to ISO 25178. 10 sites were measured at random, and the average values were taken as the values of Sa, Sz, and Sdr.

The above-mentioned multilayer film preferably has a surface roughness Sa (arithmetic mean height as described in ISO 25178) of the main surface on the substrate side of 0.05 μm or more. The upper limit is not particularly limited, and 15 μm is a substantial upper limit. If it is within the above range, the adhesiveness of the multilayer film to the base material can be reduced, and the peelability can be improved. The above-mentioned surface roughness Sa is more preferably at least 0.1 μm, further preferably at least 0.2 μm, still more preferably at least 0.3 μm, particularly preferably at least 0.4 μm, and especially preferably at least 0.5 μm. In addition, the above-mentioned multilayer film preferably has a surface roughness Sz (maximum height described in ISO 25178) of the main surface on the substrate side of 8 μm or more. The upper limit is not particularly limited, and 240 μm is a substantial upper limit. If it is within the above range, the adhesiveness of the multilayer film to the base material can be reduced, and the peelability can be improved. The above-mentioned surface roughness Sz is more preferably at least 16 μm, further preferably at least 24 μm, still more preferably at least 32 μm, particularly preferably at least 40 μm, and especially preferably at least 48 μm. In addition, it is preferable that the above-mentioned multilayer film has a surface roughness Sdr (maximum height described in ISO 25178) of the main surface on the side of the base material to be 0.05 or more. The upper limit is not particularly limited, and 15 is a substantial upper limit. If it is within the above range, the base material can be protected from damage caused by surface scratches applied to the base material or pressure applied to the base material, or the thermal insulation of the base material can be improved. The above-mentioned surface roughness Sdr is more preferably 0.1 or more, still more preferably 0.2 or more, still more preferably 0.3 or more, particularly preferably 0.4 or more, especially preferably 0.5 or more. Furthermore, the above-mentioned surface roughness Sa, Sz and Sdr are measured with a laser microscope (for example: morphological analysis laser microscope, VK-X1050, manufactured by Keynes Co., Ltd.) on the main surface of the base material side of the produced multi-layer film. The range of ×1 mm is calculated according to ISO 25178. 10 parts were measured at random, and the average values were taken as the values of Sa, Sz and Sdr.

The preferred lower limit of the average cell diameter (foam diameter) of the above-mentioned multilayer film is 0.05 μm, and the preferred upper limit is 280 μm. By setting the above-mentioned average cell diameter within this range, the protective properties against scratches on the surface of the substrate can be improved. A more preferable lower limit of the above average cell diameter is 0.5 μm, and a more preferable upper limit is 225 μm. Further, the lower limit is preferably 1.0 μm, the upper limit is 180 μm, the lower limit is 1.5 μm, the upper limit is 135 μm, the lower limit is 2.0 μm, and the upper limit is 108 μm. A preferable lower limit is 2.5 μm, and a particularly preferable upper limit is 90 μm. Furthermore, the above-mentioned average cell diameter can be measured by the following method, that is, using a laser microscope (for example: morphology analysis laser microscope, VK-X1050, manufactured by Keynes Corporation) to observe the cell wall and Observe the void and measure the size of the void.

The preferred lower limit of the thickness of the above-mentioned multilayer film is 1.0 μm, and the preferred upper limit is 300 μm. If the thickness of the foam is within the above range, both peeling and water dissolution of the foam layer can be realized. A more preferable lower limit of the thickness of the above-mentioned multilayer film is 2.0 μm, and a more preferable upper limit is 250 μm. Further, the lower limit is preferably 4.0 μm, the upper limit is 200 μm, the lower limit is 6.0 μm, the upper limit is 150 μm, the lower limit is 8.0 μm, and the upper limit is 120 μm, especially A preferable lower limit is 10.0 μm, and a particularly preferable upper limit is 100 μm. The thickness of the prepared film can be measured by using a constant pressure thickness measuring machine (eg: Teclock, PG-02J) in accordance with JIS K6783, a laser microscope (morphological analysis laser microscope, etc.) for thickness measurement, etc.

In the laminate of the present invention, the peel strength between the multilayer film and the substrate is preferably 2 N or less in a 180° peel strength test. By making the above peel strength 2 N or less, the multilayer film can be peeled from the base material. The preferable upper limit of the above-mentioned peel strength is 1.5 N, and the preferable lower limit is 0.01 N, and it is not specifically limited. The above-mentioned 180° peel strength can be measured by a method based on ISO29862:2007 or JIS Z 0237:2009. The 90° peel strength can also be measured by a method based on ISO29862:2007 or JISZ 0237:2009.

The method for producing a laminate of the present invention, the method for producing a substrate including the removal step of removing the multilayer film from the substrate, and the substrate obtained by the method for producing the substrate of the present invention are also part of the present invention. . Examples of the removal step include a method of removing the end of the multilayer film by pulling it up manually or mechanically, and a method of removing the end of the multilayer film by spraying air or the like. In addition, a method of dissolving and removing the multilayer film using a solvent such as water may also be employed. Especially when there is a step of removing the multilayer film from the base material, the role of the protective film forming aqueous solution applied for the first time is to prevent adhesion caused by direct contact between the resin and the base material in the above protective film forming step. Since the strength is increased, it is particularly preferable that the composition of the aqueous solution for forming a protective film for the first coating does not contain a resin and contains only a plasticizer and water. In particular, when the substrate is at a high temperature in the film forming step, the adhesive force increases due to the contact between the resin and the substrate in the film forming step. Therefore, it is preferable that the protective film forming aqueous solution applied for the first time does not contain resin.

A series of steps in the manufacturing method of the above-mentioned laminated body of the present invention and the manufacturing method of the base material of the present invention can be performed by a manufacturing device. Therefore, the apparatus for performing the manufacturing method of the laminated body of this invention, and the apparatus for performing the manufacturing method of the base material of this invention are also one of this invention. [Effect of Invention]

According to the present invention, it is possible to provide a method for producing a laminate capable of forming a protective film, a method for producing a base material, and a base material, the protective film being less likely to adhere to foreign matter from the base material in a production line or a transfer line.

Hereinafter, examples are disclosed to describe the present invention in more detail, but the present invention is not limited to these examples.

(Example 1) (Preparation of aqueous solution for protective film formation [for inner layer and outer layer]) Dissolve 100 parts by weight of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Industry Co., Ltd., SELVOL 203, degree of polymerization 300, degree of saponification 88 mol%), and 30 parts by weight of diglycerin as a plasticizer in 370 parts by weight of water , mixed to prepare an aqueous solution for forming a protective film [inner layer] with a resin content of 20% by weight and a plasticizer content of 6% by weight. Also, 100 parts by weight of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Industry Co., Ltd., SELVOL 103, degree of polymerization 300, degree of saponification 98.4 mol%) and 10 parts by weight of diglycerin as a plasticizer were dissolved in 890 parts by weight of water. Parts were mixed to prepare an aqueous solution for forming a protective film [for the outer layer] with a resin content of 10% by weight and a plasticizer content of 1% by weight.

，cap HN400A），作為塗料供給機器，使用壓送泵PT-10DW（ANEST IWATA公司製造），作為塗裝機器人，使用EPX-1250 DX100（安川電機公司製造）。 再者，噴霧塗佈保護皮膜形成用水溶液[內層用]時自噴槍噴出之噴出量設為10 g/30秒，保護皮膜形成用水溶液[外層用]之噴出量設定為10 g/30秒。 又，作為噴霧條件，將壓送泵之壓力設為2.0 MPa，將液壓設為0.2 MPa，將噴槍氣壓設為0.2 MPa，將塗裝機器人之塗裝速度設為50 mm/秒。 (Preparation of Protective Film [Glass Film]) A glass substrate (manufactured by Corning Inc., EagleXG 150 mm×150 mm×0.5 mm) was heated on a hot plate until the center of the glass substrate reached 300°C. Move the heated glass substrate on the spray table, and spray the obtained aqueous solution for forming a protective film [for the inner layer] on the glass substrate once when the center of the glass reaches 250°C, and then, from it The aqueous solution for forming a protective film [for the outer layer] obtained above is spray-coated once, and dried for 60 seconds in a batch type hot air circulation drying oven (set at 150°C) to obtain two layers formed on the surface of the glass substrate. [Inner layer, outer layer] Laminated body of glass film. In addition, AGB50 (manufactured by Asahi Sunac Co., Ltd., caliber 1.0 mm

, cap HN400A), as a paint supply machine, use a pressure pump PT-10DW (manufactured by ANEST IWATA), and as a painting robot, use EPX-1250 DX100 (manufactured by Yaskawa Electric). In addition, when spraying the aqueous solution for forming a protective film [for the inner layer], the spraying amount from the spray gun is set to 10 g/30 seconds, and the spraying amount of the aqueous solution for forming a protective film [for the outer layer] is set to 10 g/30 seconds . Also, as spraying conditions, the pressure of the pressure pump was set to 2.0 MPa, the hydraulic pressure was set to 0.2 MPa, the air pressure of the spray gun was set to 0.2 MPa, and the coating speed of the coating robot was set to 50 mm/sec.

(Example 2) (Production of aqueous solution for protective film formation [outer layer]) In addition to using 100 parts by weight of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Industry Co., Ltd., SELVOL 203, degree of polymerization 300, degree of saponification 88 mol%), without adding plasticizer, with the method of embodiment 1 (protective film Preparation of the aqueous solution for formation [for the inner layer]) Prepare the aqueous solution for the formation of the protective film [for the outer layer] in the same manner.

，cap HN400A），作為塗料供給機器，使用壓送泵PT-10DW（ANEST IWATA公司製造），作為塗裝機器人，使用EPX-1250 DX100（安川電機公司製造）。再者，以下實施例、比較例中，於進行噴霧塗佈之情形時，使用與上述中相同之噴槍、塗料供給機器、塗裝機器人進行噴霧塗佈。 再者，噴霧塗佈保護皮膜形成用水溶液[內層用]時自噴槍噴出之噴出量設為10 g/30秒，保護皮膜形成用水溶液[外層用]之噴出量設定為10 g/30秒。 又，作為噴霧條件，將壓送泵之壓力設為2.0 MPa，將液壓設為0.2 MPa，將噴槍氣壓設為0.2 MPa，將塗裝機器人之塗裝速度設為50 mm/秒。 (Preparation of protective film [glass film]) A glass substrate (manufactured by Corning Inc., EagleXG 150 mm×150 mm×0.5 mm) was heated on a hot plate until the center of the glass substrate reached 300°C. The heated glass substrate was moved on a spray stage, and the aqueous solution for forming a protective film obtained in Example 1 [for the inner layer] was spray-coated once on the glass substrate when the center of the glass reached 250°C. Furthermore, the obtained aqueous solution for forming a protective film [for the outer layer] was spray-coated once from above, and then dried for 60 seconds in a batch-type hot air circulation drying oven (set at 150°C) to obtain a glass substrate A laminate of two layers [inner layer, outer layer] glass film is formed on the surface. In addition, AGB50 (manufactured by Asahi Sunac Co., Ltd., caliber 1.0 mm

, cap HN400A), as a paint supply machine, use a pressure pump PT-10DW (manufactured by ANEST IWATA), and as a painting robot, use EPX-1250 DX100 (manufactured by Yaskawa Electric). In addition, in the following examples and comparative examples, when performing spray coating, spray coating was performed using the same spray gun, paint supply machine, and coating robot as above. In addition, when spraying the aqueous solution for forming a protective film [for the inner layer], the spraying amount from the spray gun is set to 10 g/30 seconds, and the spraying amount of the aqueous solution for forming the protective film [for the outer layer] is set to 10 g/30 seconds . Also, as spraying conditions, the pressure of the pressure pump was set to 2.0 MPa, the hydraulic pressure was set to 0.2 MPa, the air pressure of the spray gun was set to 0.2 MPa, and the coating speed of the coating robot was set to 50 mm/sec.

(Example 3) (Preparation of aqueous solution for protective film formation [for inner layer and outer layer]) Without adding unmodified polyvinyl alcohol, 100 parts by weight of diglycerin as a plasticizer is dissolved in 1900 parts by weight of water and mixed to prepare an aqueous solution for forming a protective film with a plasticizer content of 5% by weight [for the inner layer] . Also, 100 parts by weight of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Industry Co., Ltd., SELVOL 203, degree of polymerization 300, degree of saponification 88 mol%) and 15 parts by weight of diglycerin as a plasticizer were dissolved in 385 parts by weight of water. 20% by weight of resin and 3% by weight of plasticizer to prepare an aqueous solution for forming a protective film [for the outer layer].

(Production of protective film [glass film]) A glass substrate (manufactured by Corning Inc., EagleXG 150 mm×150 mm×0.5 mm) was heated on a heating plate until the center of the glass substrate reached 400°C. The heated glass substrate is moved on a spray stage, and the obtained aqueous solution for forming a protective film [for the inner layer] is spray-coated once on the glass substrate when the center of the glass reaches 350°C, and then The aqueous solution for forming a protective film [for the outer layer] obtained above was spray-coated once, and then dried for 60 seconds in a batch type hot air circulation drying oven (set at 150°C) to obtain 2 layers formed on the surface of the glass substrate. Layer [inner layer, outer layer] laminated body of glass film. In addition, the discharge amount from the spray gun is shown in Table 1.

(Example 4) Use 100 parts by weight of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Industry Co., Ltd., SELVOL 205, degree of polymerization 500, degree of saponification 88 mol%) instead of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Industry Co., Ltd., SELVOL 203 , degree of polymerization 300, degree of saponification 88 mol%) 100 parts by weight, the addition amount of plasticizer, resin content, plasticizer content are made as shown in table 1, except that, with the same method as embodiment 3 Method Make an aqueous solution for forming a protective film [for the outer layer]. Except for using the obtained aqueous solution for forming a protective film [for the outer layer], in the same manner as in Example 3, two layers were formed on the surface of a glass substrate (manufactured by Corning Incorporated, EagleXG 150 mm×150 mm×0.5 mm) [Inner layer, outer layer] Laminated body of glass film.

(Example 5) Using 18 parts by weight of glycerin instead of 15 parts by weight of diglycerol as a plasticizer, the amount of plasticizer added, resin content, and plasticizer content are set as shown in Table 1. In addition, the same method as in Example 3 was used. Method Make an aqueous solution for forming a protective film [for the outer layer]. A laminate in which a glass film was formed was produced in the same manner as in Example 3 except that the obtained aqueous solution for forming a protective film [for the outer layer] was used.

(Example 6) Without adding unmodified polyvinyl alcohol, 100 parts by weight of glycerin as a plasticizer was dissolved in 1940 parts by weight of water, and mixed to prepare an aqueous solution for forming a protective film with a plasticizer content of 3% by weight [for the inner layer] . Use 100 parts by weight of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Industry Co., Ltd., SELVOL 205, degree of polymerization 500, degree of saponification 88 mol%) instead of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Industry Co., Ltd., SELVOL 203 , degree of polymerization 300, degree of saponification 88 mol%) 100 parts by weight, use 18 parts by weight of glycerin instead of 15 parts by weight of diglycerin as plasticizer, set the amount of plasticizer, resin content, and plasticizer content as Except as shown in Table 1, in the same manner as in Example 3, an aqueous solution for forming a protective film [for the outer layer] was prepared. A laminate on which a glass film was formed was produced in the same manner as in Example 3 except that the obtained aqueous solution for forming a protective film [for the inner layer] and the aqueous solution for forming a protective film [for the outer layer] were used.

(Embodiments 7-12) Except that the composition of the aqueous solution for forming a protective film [for the inner layer] and the aqueous solution for forming a protective film [for the outer layer], the amount of spray from the spray gun, and the temperature at the time of spray coating were set as shown in Table 1, the 3. In the same way, a laminate with a glass film is formed.

(comparative example 1) Without using 100 parts by weight of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Industry Co., Ltd., SELVOL 203, degree of polymerization 300, degree of saponification 88 mol%), only diglycerin as a plasticizer was produced as shown in Table 1. Aqueous solution (plasticizer content 5% by weight). A glass substrate (manufactured by Corning Inc., EagleXG 150 mm×150 mm×0.5 mm) was heated on a heating plate until the center of the glass substrate reached 300°C. Move the heated glass substrate on the spray table, and spray the obtained aqueous solution on the glass substrate once when the central part of the glass reaches 350°C, and use a batch type hot air circulation drying oven (set at 150°C ) for 60 seconds to obtain a laminate with a glass film formed on the surface of the glass substrate. Furthermore, the obtained glass film consists only of diglycerin and moisture as a plasticizer.

(comparative example 2) In the same manner as in Comparative Example 1, except that only diglycerin as a plasticizer was made into an aqueous solution as shown in Table 1, an aqueous solution for forming a protective film with a plasticizer content of 40% by weight, and a laminate with a glass film were prepared. . The film is composed only of diglycerin as a plasticizer and water.

(comparative example 3) Except for using glycerin instead of diglycerin as the plasticizer, and preparing an aqueous solution as shown in Table 1, an aqueous solution for forming a protective film with a plasticizer content of 3% by weight and a laminate with a glass film were prepared in the same manner as in Comparative Example 1. . The film is composed only of glycerin and water as a plasticizer.

(comparative example 4) Except that only glycerin as a plasticizer was made into an aqueous solution as shown in Table 1, an aqueous solution for forming a protective film having a plasticizer content of 20% by weight and a laminate with a glass film were prepared in the same manner as in Comparative Example 3. The film is composed only of glycerin and water as a plasticizer.

(comparative example 5) Using 100 parts by weight of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Industry Co., Ltd., SELVOL 203, degree of polymerization 300, degree of saponification 88 mol%), the amount of plasticizer added and the resin concentration are set as shown in Table 1 , except that, in the same manner as in Comparative Example 1, an aqueous solution for forming a protective film and a laminate in which a glass film was formed were produced.

(comparative example 6) Use 100 parts by weight of unmodified polyvinyl alcohol (polymerization degree 500, saponification degree 88 mol%) instead of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Industry Co., Ltd., SELVOL 203, polymerization degree 300, saponification degree 88 mol%) %) 100 parts by weight, except that the addition amount of the plasticizer (diglycerin) and the resin concentration were as shown in Table 1, a laminate with a glass film was produced in the same manner as in Comparative Example 1.

＜Evaluation＞ The following evaluations were performed on the aqueous solution for forming a protective film (aqueous solution) obtained in Examples and Comparative Examples, and the laminate on which the glass film was formed. The results are shown in Table 1 and Table 2.

1. Evaluation of aqueous solution for protective film formation (Contact angle measurement) Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DMo-502) and analysis software FAMAS (manufactured by Kyowa Interface Science Co., Ltd.), by the θ/2 method (A half-angle method), at a temperature of 23°C and a humidity of 60%R /H for contact angle measurement. As measurement conditions, an appropriate amount of liquid was set to 2 μL, a glass (TEMPAX Float, manufactured by SCHOTT Co., Ltd.) with a thickness of 0.5 mm was used as a contact angle measurement substrate, and the waiting time before measurement was set to 100 msec in the time-lapse measurement mode. The measurement interval was 1000 msec, and the measurement was repeated 5 times. In the evaluation results, the data of 5 times of 4100 msec were averaged as the measurement results. Furthermore, if the contact angle between the aqueous solution for forming a protective film and the adherend is kept low, shrinkage and the like can be suppressed during film formation, and a homogeneous protective film free from pinholes and the like can be formed.

(Viscosity determination) The prepared aqueous solution for forming a protective film was divided into mayonnaise bottles, the lids were closed, and cured at a temperature of 23° C. and a humidity of 60% RH for 2 days (48 hours). Using a rotary viscometer (manufactured by Toki Sangyo Co., Ltd., TVC-10), measure the viscosity of the aqueous solution for forming a protective film after curing by the method in accordance with JIS K7117-1 under the conditions of temperature 23°C and humidity 60%RH evaluate. Furthermore, by controlling the viscosity of the aqueous solution for forming a protective film, the film can be easily formed. By making the above viscosity not too high, especially in steps such as spray film formation, stringing can be produced and a good film can be obtained, thereby preventing surrounding pollution. By making the above-mentioned viscosity not too low, it is possible to prevent the homogeneity of the film from being damaged or the drying time being too long due to excessively large foaming diameters.

2. Evaluation of film and laminate (thickness evaluation) The glass film was peeled off from the obtained laminate with the glass film formed thereon, and the thickness of the glass film was measured using a constant-pressure thickness measuring machine (for example: manufactured by Teclock Co., Ltd., PG-02J) in accordance with JIS K6783. When it is difficult to peel off, measure the thickness of the laminate with the glass film formed on it using the above-mentioned constant pressure thickness measuring machine, subtract the thickness of the glass substrate previously measured by the same method, and use the obtained value as the thickness. Also, as shown in the comparative example, when the film is liquid, use a laser microscope (morphological analysis laser microscope, VK-X1050, manufactured by Keynes Corporation) to measure the range of 1 mm × 1 mm, and the obtained The average thickness is taken as the thickness of the film. Furthermore, by making the thickness of the film not too thin, the performance as a protective film can be exhibited, and by not making the thickness of the film not too thick, it is possible to prevent problems such as an increase in cost and a long drying time.

(Surface roughness) The surface roughness Sa, Sz, and Sdr are obtained by peeling off the glass film from the laminate formed with the glass film. Interface side surface), respectively, using a laser microscope (for example: Morphological Analysis Laser Microscope, VK-X1050, manufactured by Keynes Co., Ltd.) to measure the range of 1 mm × 1 mm. Based on the measured values obtained, each surface roughness was calculated according to ISO 25178. Ten sites were randomly measured, and the average values were taken as the values of Sa, Sz and Sdr. Furthermore, by controlling the surface roughness, it is possible to suppress sticking when stacking, storing or transporting the glass (laminated body) on which the film is laminated.

(coverage rate) The obtained glass film was peeled off from the glass, and 10 parts were measured in an area of 1 mm × 1 mm using a laser microscope (for example: morphological analysis laser microscope VK-X1050, manufactured by Keynes Co., Ltd.). The ratios were averaged and evaluated. ◎: More than 90% of the area is covered with film ○: Film coating is carried out on the area of less than 90% and more than 80% △: Film coating is carried out on the area of less than 80% and more than 70% ×: Film coverage is less than 70% Furthermore, by increasing the coating ratio of the film, it is possible to suppress the adhesion of fine debris suspended in the glass manufacturing process to the surface of the glass in the non-coated area of the film-laminated glass.

(foaming) Peel off the glass film of the obtained laminate, check the cross-section of the peeled film with a laser microscope (for example: Morphological analysis laser microscope VK-X1050, manufactured by Keynes Corporation), check whether there is foaming, and evaluate according to the following criteria . ○: Foaming ×: Foaming was not observed

(foam diameter) The glass film of the obtained laminate was cut, and cut along a plane parallel to the thickness direction with a razor blade. Thereafter, the maximum cell diameter in the normal direction was measured on a cut surface in the thickness direction with a laser microscope (eg, morphology analysis laser microscope VK-X1050, manufactured by Keynes Corporation). This operation was repeated 10 times while changing the measurement site, and the average value of the observed foam diameters was defined as the average bubble diameter. In addition, about the foam diameter of each bubble, it was set as the diameter of the inscribed circle which becomes the largest diameter when drawing the inscribed circle inscribed with respect to the observed bubble. The obtained foam diameter (average cell diameter) was evaluated based on the following criteria. ◎: The foam diameter is more than 20% of the thickness of the glass film ○: The diameter of the foam is less than 20% and more than 5% of the thickness of the glass film △: The foam diameter is less than 5% and more than 1% of the thickness of the glass film ×: The diameter of the foam does not reach 1% of the thickness of the glass film

(density) Using a laser microscope (manufactured by Olympus, OLS4100, analysis software is Lest), an image of a 3 mm square film was obtained with an objective lens of 20 times and in high-precision mode, and the volume was calculated. Next, the measured film of 3 mm square was peeled off from the substrate, collected, and weighed with a weighing meter (manufactured by Mettler Toledo, XPE56). The obtained weight was divided by the volume to calculate the density. Furthermore, by controlling the foaming diameter of the film or the foaming ratio (density) of the film, the impact on the manufactured glass during transportation and transportation can be alleviated, and surface damage or cracking can be suppressed.

(crystallinity) For the test piece made of the glass film of the obtained laminate, use an XRD diffraction device (manufactured by Rigaku, Rint2500) to measure the diffracted light when the X-ray incident angle 2θ=2°～40°, according to the peak and The degree of crystallinity was calculated from the strength of the halo, and evaluated according to the following criteria. Furthermore, the measurement conditions are as follows, the X-ray tube is set to CuKα ray (λ=1.54 Å), the X-ray output is set to 40 kV200 mA, the scanning method is set to step scanning (FT method), and the step size is set to 0.02. Set to 2 seconds of reflection strength. In addition, the crystallinity was measured by peeling the glass film from the laminate, and measuring the surface in close contact with the glass as the "glass interface", and measuring the opposite surface as the "surface". In the case of a two-layer structure, similarly, the surface in close contact with the glass is measured as the "glass interface", and the opposite surface is measured as the "surface". High: more than 50% Medium: less than 50% and more than 30% Low: Less than 30% Furthermore, when the crystallinity is low, the surface of the substrate side of the film is plasticized, the adhesion to the substrate becomes low, and it is easy to peel off or remove by water solution. The crystallinity on the air interface (surface) side of the film is relatively high. When the value is high, the adhesiveness becomes low, and it can suppress adhesion when laminated in the storage or transportation of film laminated glass.

(Peel and Removable) [Releasability] For the obtained laminate (150 mm×150 mm), a glass cutter (manufactured by MITSUBOSHI DIAMOND, MS500) was used from the film side, and a glass cutting tool (manufactured by MITSUBOSHI DIAMOND, Mrcs-APIO "Mrcs- ADP030065080-115000000A4"), cut the perimeter 10 mm, and make a 130 mm square sample. Thereafter, an adhesive tape (manufactured by Sekisui Chemical Industry Co., Ltd., Cellotape (registered trademark), No. 252, 24 mm width) was attached to the corner, peeled at an angle of about 135°, and evaluated according to the following criteria. ◎: The film can be completely peeled off ○: Although a part of the film remains, the film can be peeled off by one peeling without the film being torn at all △: A part is broken, but the film can be peeled off by peeling off multiple times ×: The film was broken and could not be peeled off Furthermore, if the peelability of the film is good, the cleaning step in the subsequent steps can be implemented more easily and concisely in glass manufacturing, and the improvement of manufacturing efficiency caused by short production pitch and the consequent reduction of power consumption can be obtained. The effect of reducing the environmental impact caused by the reduction, or the reduction of washing water, etc.

[180°peel strength] In order to evaluate the adhesive force between the prepared film and the glass substrate, the obtained laminate (150 mm×150 mm) was cut to make a 25 mm×150 mm glass sample with the film as a sample for the 180° peel test. In addition, the cutting method is the same as the case of the said [peelability]. After attaching the adhesive tape with the base material (with product number Splicing tape NO.642, manufactured by Teraoka Seisakusho) to the entire surface of the film to apply the substrate, the film with the adhesive tape as the substrate and the adhesive tape are used together. The 180° peel strength was measured with a material testing machine (RTF-2430, manufactured by GL Science). The measurement method is based on ISO29862:2007 or JIS Z 0237:2009. Furthermore, when peeling off the film surface, hold one end of the tape in such a way that the back side of the substrate surface overlaps, fold back 180°, peel off the film surface by 25 mm, and fix the peeled part of the film surface on the jig at the lower side of the testing machine , Fix the adhesive tape attached to the base material on the jig on the upper side. The evaluation was carried out under the conditions of 300 mm/sec, temperature 25°C, and humidity 50%. Furthermore, if the peeling strength can be set low, the peeling of the film can be performed more easily.

[Water Solubility] From the obtained laminate, 1 cm ² of the glass film was peeled off, immersed in a beaker filled with 10°C water, and the water solubility [10°C water solubility] was evaluated according to the following criteria. In addition, the water solubility [95 degreeC water solubility] at the time of adding the water of 95 degreeC was also evaluated. ○: Dissolved within 60 seconds △: Dissolved within 61 seconds to 120 seconds X: Not dissolved within 120 seconds Furthermore, if the water solubility of the film is good, even if there is peeling residue on the glass, it can be used in the subsequent steps The protective film is easily and completely removed from the glass surface in the cleaning step. Furthermore, when static electricity generated by peeling becomes a problem, by dissolving it without peeling, it is also possible to remove the film without static electricity.

(residue after film removal) The residue after removing the glass film of the obtained laminate from the glass substrate was evaluated. Furthermore, the removal of the glass film is carried out by the following three methods, namely: "1. Removal by peeling", "2. Removal by water washing", "3. After peeling, by water washing Clean removal (washing with water after stripping)". [1. Removal by stripping] The obtained laminate (150 mm x 150 mm) was cut to make a glass sample with a glass film of 10 mm x 10 mm, and the glass film was removed by peeling off. [2. Removal by washing with water] For the glass film surface of the obtained laminate (150 mm×150 mm), spray and irradiate steam at 85-90°C with a maximum vapor pressure of 0.2 MPa and 2 L/min from a nozzle with a slit width of 0.1 mm, and then heat it at 90°C. Wash it with warm water, and then use a slit nozzle to wash it with room temperature water to remove the glass film. [3. Removal by washing with water after peeling (washing with water after peeling)] The obtained laminate (150 mm x 150 mm) was cut to make a glass sample with a glass film of 10 mm x 10 mm, and the glass film was removed by peeling off. Then, for the sample whose glass film was removed by peeling, steam at 85-90°C was sprayed from a nozzle with a maximum vapor pressure of 0.2 MPa and 2 L/min from a nozzle with a slit width of 0.1 mm, and then washed with warm water at 90°C , followed by washing with normal temperature water using a slit nozzle.

[XPS evaluation] For the glass surface of the part where "1. Removal by peeling", "2. Removal by water washing" and "3. Removal by water washing after peeling (water washing after peeling)" were performed, The composition of the residue on the outermost surface was quantified by X-electron spectroscopy (XPS, PHI5000 VersaProbe II, manufactured by ULVAC-PHI). The measurement conditions are as follows, using monochromatic AlKα (1486.6 eV) as a light source, measuring at a photoelectron grazing angle of 45 degrees, and an X-ray beam diameter of 200 μm. In addition, regarding the glass substrate of the same type as the substrate used for production, "1. Removal by peeling", "2. Removal by washing with water" and "3. After peeling, rinse with water" were performed in the same manner as above. Removal by washing (washing with water after stripping)", as a reference sample. Carry out the XPS evaluation of the glass surface, calculate the carbon atomic weight (%) based on the carbon atomic weight (atom%) of the reference sample [(measured carbon atomic weight/carbon atomic weight of the reference sample)×100], and evaluate according to the following criteria. Furthermore, the carbon atomic weight (%) based on the reference sample is proportional to the amount of residual film that cannot be seen visually after removal of the glass film. The smaller it is, the easier it is to clean the glass surface after film removal. Achieve cleanliness. ◎: Carbon atomic weight is 150% or less ○: Carbon atomic weight exceeds 150% and is 250% or less △: Carbon atomic weight exceeds 250% and is 400% or less ×: Carbon atomic weight exceeds 400% Furthermore, if the carbon residue after the removal of the film is less, the amount of detergent used is reduced, etc., and the cleaning step can be implemented more easily and concisely, and the improvement of manufacturing efficiency caused by shortening the production pitch can be obtained. The effect of reducing the environmental impact caused by the reduction of electricity usage, or the reduction of washing water, etc. In addition, the brush cleaning step for removing organic residues on the glass surface can be easily performed, and surface damage caused by brush cleaning can be reduced.

(storage) The two obtained laminates (150 mm×150 mm) were stacked so that the glass film surfaces were in close contact with each other, and 3.0 kg of SUS plates of the same size or more were placed on top of them, and placed in an environment of 25°C and 50%RH for 1 week. Thereafter, the two laminates were peeled off to confirm the breakage rate of the glass film, and evaluated according to the following criteria. ◎: The damage rate of the glass film is less than 10% ○: The damage rate of the glass film is more than 10% and less than 30% △: The damage rate of the glass film is more than 30% and less than 50% ×: The damage rate of the glass film exceeds 50% Furthermore, if the storage property is good, more glass can be laminated for temporary storage, and the efficiency of glass manufacturing can be improved.

(Foreign matter exclusion effect) On the glass film side of the obtained laminate, 0.05 g of silica particles (average particle diameter: 3 μm) was dry-sprayed to adhere to the film. Next, the film was peeled off, and the presence or absence of silica particles in the central 5 cm square of the 15 cm square glass was checked with an optical microscope, and evaluated according to the following criteria. ◎: Less than 10 silica particles confirmed ○: 11 to 20 silica particles confirmed △: 21 to 50 silica particles confirmed ×: More than 51 silica particles were confirmed Furthermore, if the foreign matter removal effect of the film is high, the glass surface can be protected from tiny glass fragments generated when the glass is broken or transported incorrectly when the glass is dropped or scattered during glass manufacturing. Glass shards adhering to the glass surface are restricted in quality control, and if it exceeds the standard, it will be regarded as a defective product and cannot be made into a product.

(Surface Protection: Scratch Resistance) Dry-spray 0.05 g of silica particles (average particle diameter: 3 μm) on the glass film side of the obtained laminate to adhere to the film, and then laminate a glass substrate of the same size (manufactured by Corning Incorporated, EagleXG 150) mm×150 mm×0.5 mm), rub against each other in the surface direction. Thereafter, the film was peeled off, the surface was observed, and evaluation was performed based on the following criteria. ○: No scratches on the surface ×: There is scratch damage on the surface Furthermore, if there are many tiny glass debris generated in the manufacturing process attached to the surface, the attached debris will move during transportation, stacking and storage, etc., causing damage to the glass surface and secondary damage, which will greatly affect the yield. Influence.

(environmental adaptability) For the peeled film, evaluate whether it has biodegradability in soil. In the case of biodegradability in soil, it can be said to be environmentally friendly. Furthermore, the film that can be removed by washing with water can be completely dissolved in water, and can be disposed of in ordinary sewage like the film wrapping the gel ball lotion added with lotion, so it is environmentally friendly. ○: Biodegradable in soil ×: No biodegradability in soil Furthermore, if the film is biodegradable, the removed protective film can be discarded without exacerbating the world's ever-increasing waste plastic problem.

[Table 1] aqueous solution Film making steps type polyvinyl alcohol Plasticizer Content (weight%) Contact angle (°) Viscosity (mPa・s) Discharge amount(g/30 sec) glass type Coating temperature (°C) drying step layer composition Degree of Saponification (Mole%) Polymerization Amount added (parts by weight) type Amount added (parts by weight) resin Plasticizer Example 1 Inner layer 88 300 100 Diglycerol 30 20 6 48.1 216.0 10.0 Eagle 250 implement multi-layer For outer layer 98.4 300 100 Diglycerin 10 10 1 45.5 176.0 10.0 Example 2 Inner layer 88 300 100 Diglycerin 30 20 6 48.1 216.0 10.0 Eagle 250 implement multi-layer For outer layer 88 300 100 - 0 20 0 44.9 192.0 10.0 Example 3 Inner layer - - 0 Diglycerol 100 0 5 45.5 1.6 8.0 Eagle 350 implement multi-layer For outer layer 88 300 100 Diglycerol 15 20 3 47.9 203.0 12.0 Example 4 Inner layer - - 0 Diglycerol 100 0 5 45.5 1.6 8.0 Eagle 350 implement multi-layer For outer layer 88 500 100 Diglycerol 15 15 2.25 47.3 148.0 12.0 Example 5 Inner layer - - 0 Diglycerol 100 0 5 45.5 1.6 8.0 Eagle 350 implement multi-layer For outer layer 88 300 100 glycerin 18 20 3.6 47.69 201.0 12.0 Example 6 Inner layer - - 0 glycerin 100 0 3 43.3 1.2 8.0 Eagle 350 implement multi-layer For outer layer 88 500 100 glycerin 18 15 2.7 46.8 137.0 12.0 Example 7 Inner layer 98.4 300 100 Diglycerol 10 10 1 45.5 176.0 10.0 Eagle 200 implement multi-layer For outer layer 88 300 100 Diglycerin 30 20 6 48.1 216.0 10.0 Example 8 Inner layer 88 300 100 - 0 20 0 44.9 192.0 10.0 Eagle 150 implement multi-layer For outer layer 88 300 100 Diglycerin 30 20 6 48.1 216.0 10.0 Example 9 Inner layer - - 0 Diglycerin 100 0 5 45.5 1.6 8.0 Eagle 350 implement multi-layer For outer layer 88 300 100 Diglycerin 30 20 6 48.1 216.0 12.0 Example 10 Inner layer - - 0 Diglycerin 100 0 5 45.5 1.6 8.0 Eagle 350 implement multi-layer For outer layer 88 500 100 Diglycerin 25 15 3.75 47.3 148.0 12.0 Example 11 Inner layer - - 0 Diglycerin 100 0 5 45.5 1.6 8.0 Eagle 350 implement multi-layer For outer layer 88 300 100 glycerin 15 20 3 47.69 201.0 12.0 Example 12 Inner layer - - 0 glycerin 100 0 3 43.3 1.2 8.0 Eagle 350 implement multi-layer For outer layer 88 500 100 glycerin 15 10 1.5 46.8 137.0 12.0 Comparative example 1 - - - 0 Diglycerin 100 0 5 45.5 1.6 20.0 Eagle 350 implement single layer Comparative example 2 - - - 0 Diglycerol 100 0 40 50.3 7.2 5.0 Eagle 350 implement single layer Comparative example 3 - - - 0 glycerin 100 0 3 43.3 1.2 20.0 Eagle 350 implement single layer Comparative example 4 - - - 0 glycerin 100 0 20 48.6 2.1 20.0 Eagle 350 implement single layer Comparative Example 5 - 88 300 100 - 0 0.05 0 38.1 2.5 20.0 Eagle 350 implement single layer Comparative example 6 - 88 500 100 Diglycerin 50 0.05 0.025 38.8 2.7 20.0 Eagle 350 implement single layer

[Table 2] film evaluation Laminate evaluation thickness Surface Roughness (Major Surface Opposite to Substrate) Surface roughness (substrate side main surface) coverage Foaming Foam diameter Density (g/cm ³ ) Crystallinity Peeling, removal Residue after removal Storage (adhesion) Before peeling Foreign matter removal effect Surface protection (scratch resistance) Environmental adaptation Measured value (μm) Sa (μm) Sz (μm) Sdr Sa (μm) Sz (μm) Sdr glass interface surface Stripping 180° Peel Strength[N/25 mm] 10℃ Water Solubility 95℃ water soluble peel off washed Peel off and wash Example 1 28.8 2.54 66.70 0.82 0.57 48.70 0.66 ◎ ○ ◎ 0.44 Low high ○ 0.198 x ○ △ ○ ○ ◎ ○ ○ ○ Example 2 39.6 2.96 69.50 0.88 0.61 50.55 0.69 ◎ ○ ◎ 0.34 Low high ○ 0.226 ○ ○ △ ○ ○ ◎ ○ ○ ○ Example 3 26.4 3.64 79.70 1.05 0.74 55.34 0.79 ◎ ○ ◎ 0.39 Low middle ◎ 0.227 ○ ○ ◎ ◎ ◎ 〇 ◎ ○ ○ Example 4 36.8 8.95 130.08 3.45 2.89 92.22 0.91 ◎ ○ ◎ 0.32 Low middle ◎ 0.198 ○ ○ ○ ◎ ◎ 〇 ◎ ○ ○ Example 5 20.7 3.75 81.20 1.18 0.76 56.90 0.81 ◎ ○ ◎ 0.4 Low high ◎ 0.131 ○ ○ △ ◎ ◎ △ ◎ ○ ○ Example 6 29.2 9.12 130.45 3.67 2.78 92.40 0.90 ◎ ○ ◎ 0.34 Low high ◎ 0.121 ○ ○ △ ◎ ◎ △ ◎ ○ ○ Example 7 27.3 2.29 53.36 0.70 0.54 41.40 0.53 ◎ ○ ○ 0.46 high Low ○ 0.288 x ○ △ ○ ○ ○ ○ ○ ○ Example 8 37.5 2.81 63.94 0.84 0.56 46.27 0.62 ◎ ○ ◎ 0.36 high Low ○ 0.274 ○ ○ △ ○ ○ ○ ○ ○ ○ Example 9 25.9 3.57 77.31 1.04 0.76 57.55 0.81 ◎ ○ ◎ 0.39 Low Low ◎ 0.216 ○ ○ ◎ ◎ ◎ △ ◎ ○ ○ Example 10 35.8 8.86 126.18 3.31 2.83 94.06 0.94 ◎ ○ ◎ 0.33 Low Low ◎ 0.199 ○ ○ ○ ◎ ◎ △ ◎ ○ ○ Example 11 21.8 3.83 85.26 1.24 0.79 58.04 0.85 ◎ ○ ◎ 0.38 Low Low ◎ 0.145 ○ ○ ○ ◎ ◎ △ ◎ ○ ○ Example 12 30.1 9.58 136.97 3.78 2.81 91.48 0.93 ◎ ○ ◎ 0.33 Low Low ◎ 0.132 ○ ○ ○ ◎ ◎ ○ ◎ ○ ○ Comparative example 1 2.4 0.96 2.5 1.12 x x x 1.3 x ○ ○ ○ x x Comparative example 2 19.4 3.88 22.5 1.04 x x x 1.3 x ○ ○ ○ x x Comparative example 3 1.5 0.53 1.4 1.06 x x x 1.3 x ○ ○ ○ x x Comparative example 4 9.7 2.91 10.8 1.09 x x x 1.3 x ○ ○ ○ x x Comparative Example 5 x x x 1.3 x ○ ○ ○ x x Comparative example 6 x x x 1.3 x ○ ○ ○ x x [Industrial availability]

According to the present invention, it is possible to provide a method for producing a laminate capable of forming a protective film, a method for producing a base material, and a base material, the protective film being less likely to adhere to foreign matter from the base material in a production line or a transfer line.

none

none

Claims (15)

A method for manufacturing a laminate, the laminate having a substrate and a multi-layer film, the method for producing the laminate includes a film forming step, the film forming step is formed by coating the substrate with protective films having two or more different compositions A multi-layer film is formed with an aqueous solution. The method of manufacturing a laminate according to Claim 1, wherein at least one selected from the group consisting of adhesiveness, protection, and peelability of the multilayer film can be adjusted. The method for producing a laminate according to claim 1 or 2, wherein the aqueous solution for forming a protective film having two or more different compositions is continuously applied. The method for producing a laminate according to any one of claims 1 to 3, wherein in the film forming step, the temperature of the substrate is 0°C to 400°C. The method for producing a laminate according to any one of claims 1 to 4, which includes a substrate forming step of forming a substrate, and the substrate forming step and the film forming step are performed continuously. The method for producing a laminate according to any one of claims 1 to 5, wherein the aqueous solution for forming a protective film in the first coating contains a plasticizer and water. The method for producing a laminate according to any one of claims 1 to 6, wherein any one of the plurality of protective film-forming aqueous solutions applied for the second time or thereafter contains polyvinyl alcohol resin and water. The method for producing a laminate according to any one of claims 1 to 7, wherein the aqueous solution for forming a protective film applied in the first application does not contain polyvinyl alcohol resin, or the aqueous solution for forming a protective film applied in the first application contains no polyvinyl alcohol resin. The polyvinyl alcohol resin content is less than the polyvinyl alcohol resin content of the protective film forming aqueous solution applied for the second time or thereafter. The method for producing a laminate according to any one of Claims 1 to 8, wherein the aqueous solution for forming a protective film applied for the first time has more plasticizer content than the aqueous solution for forming a protective film applied for the second time or thereafter. The plasticizer content of the aqueous solution. The method for producing a laminate according to any one of Claims 1 to 9, wherein the aqueous solution for forming a protective film applied in the first application has a plasticizer content of 0.1 to 80% by weight and a water content of 20 to 99.9% by weight . The method for producing a laminate according to any one of Claims 1 to 10, wherein the polyvinyl alcohol resin content of any of the aqueous solutions for forming a protective film applied for the second time or thereafter is 0.1 to 50% by weight, The plasticizer content is 0.1 to 50% by weight, and the water content is 10 to 99.8% by weight. A method of manufacturing a substrate, comprising the method of manufacturing a laminate according to any one of Claims 1 to 11, and a removal step of removing the multilayer film from the substrate. A substrate, which is obtained by the manufacturing method of the substrate according to claim 12. An apparatus for carrying out the method for manufacturing a laminate according to any one of Claims 1 to 11. A device for performing the manufacturing method of the substrate of claim 12.