Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
  • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
  • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
  • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic

Definitions

• the present invention relates to a resin composition for forming a protective film, a protective film and a laminate.
• 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 glass products.
• Patent Document 2 describes a method of protecting the surface of glass by covering it with a polyvinyl alcohol film.
• the present invention provides a protective film-forming resin composition capable of forming a protective film to which foreign matter derived from a substrate is less likely to adhere in a production line or a transportation line, and at the same time, exhibiting high peelability of the protective film. , to provide protective coatings and laminates.
• the present disclosure (1) is a protective film-forming resin composition used for forming a protective film on a substrate, which contains at least one selected from the group consisting of a polyvinyl alcohol resin, a plasticizer, and water. , a resin composition for forming a protective film.
• the present disclosure (2) is the protective film-forming resin composition according to the present disclosure (1), which has a viscosity of 1 mPa ⁇ s or more and 3 Pa ⁇ s or less when measured with a rotary viscometer.
• the present disclosure (3) is a protective film-forming resin composition according to the present disclosure (1) or (2), which has a contact angle of 10 ° or more and 75 ° or less with a glass substrate at a temperature of 23 ° C. and a humidity of 60% RH.
• the plasticizer contains 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.
• a protective film-forming resin composition according to any one of (1) to (3) of the present disclosure.
• the present disclosure (5) is a protective film comprising the protective film-forming resin composition according to any one of the present disclosure (1) to (4).
• the present disclosure (6) is the protective coating according to the present disclosure (5), wherein the main surface opposite to the substrate of the protective coating has a surface roughness Sa of 0.1 ⁇ m or more and 30 ⁇ m or less.
• the present disclosure (7) is the protective coating according to the present disclosure (5) or (6), wherein the surface roughness Sz of the main surface opposite to the substrate of the protective coating is 10 ⁇ m or more and 300 ⁇ m or less.
• the present disclosure (8) is the protective film according to any one of the present disclosure (5) to (7), wherein the surface roughness Sdr of the main surface opposite to the substrate of the protective film is 0.1 or more and 30 or less. is.
• the present disclosure (9) is the protective coating according to any one of the present disclosure (5) to (8), wherein the substrate-side main surface of the protective coating has a surface roughness Sa of 0.05 ⁇ m or more and 15 ⁇ m or less. .
• the present disclosure (10) is the protective coating according to any one of the present disclosure (5) to (9), wherein the substrate-side main surface of the protective coating has a surface roughness Sz of 8 ⁇ m or more and 240 ⁇ m or less.
• the present disclosure (11) is the protective coating according to any one of the present disclosure (5) to (10), wherein the substrate-side main surface of the protective coating has a surface roughness Sdr of 0.01 or more and 15 or less.
• Disclosure (12) is a laminate having a protective coating according to any one of Disclosures (5) to (11) and a substrate.
• the present disclosure (13) is the laminate according to the present disclosure (12), wherein the protective coating further has a plasticizer layer on the substrate side.
• the present disclosure (14) provides that the plasticizer layer does not contain a polyvinyl alcohol resin, or the polyvinyl alcohol resin content of the plasticizer layer is less than the polyvinyl alcohol resin content of the protective film, the present disclosure (13 ).
• the present disclosure (15) is a laminate according to any one of the present disclosure (12) to (14), wherein the peel strength between the protective film and the substrate is 2.5 N / 25 mm or less in a 180 ° peel strength test. is. The present invention will be described in detail below.
• a polyvinyl alcohol resin and a resin composition containing at least one selected from the group consisting of a plasticizer and water are used to form a protective film, thereby improving production lines and transportation.
• the inventors have found that it is possible to form a protective film to which foreign matter originating from the base material is less likely to adhere, leading to the completion of the present invention.
• the present invention is used for forming a protective film on a substrate.
• the substrate include glass, plastic substrates (organic polymer substrates), metal substrates, composites of glass/plastics/metal (printed wiring boards, etc.), and the like.
• the glass include, but are not limited to, soda-lime glass, alkali-free glass, borosilicate glass, fused quartz, and the like.
• the present invention can be particularly preferably used for thin glass for high-definition liquid crystal, and for example, the thickness is preferably 0.01 to 1.2 mm, more preferably 0.05 to 1.0 mm, further preferably 0.05 to 1.0 mm.
• UTG Ultra-Thin Glass
• a protective film can be applied without applying a load to a base material such as a glass substrate, and it can be removed with water without peeling off during removal, so that the base material is a very thin glass. Even when it is a substrate, it is suitably used as a protective film.
• the protective film-forming resin composition of the present invention it is possible not only to easily form a protective film on the glass surface of a TFT liquid crystal, but also to dissolve it in water without peeling off when removing it, so static electricity is not generated. , It does not cause static electricity trouble of TFT liquid crystal.
• the plastic substrate include, but are not limited to, a polycarbonate plate and a poly(meth)acrylic resin plate.
• the poly(meth)acrylic resin plate include a polymethyl(meth)acrylate plate.
• the metal substrate examples include, but are not limited to, 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. Alternatively, a coated steel plate of a car or the like may be used. Furthermore, by using a printed wiring board (PWB) as a base material, it can be used as a PWB protective material, particularly as an exposure protective material. Regardless of which base material is used, it is not incorporated into the final product, but can be particularly preferably used as a protective material between steps in the base material manufacturing process or as a temporary protective material on the premise of removal.
• PWB printed wiring board
• the protective film-forming resin composition of the present invention contains a polyvinyl alcohol resin.
• a polyvinyl alcohol resin By using the polyvinyl alcohol resin, it is possible to make the protective film water-soluble. In addition, soil biodegradability can be imparted.
• the saponification degree of the polyvinyl alcohol resin has a preferable lower limit of 50 mol% and a preferable upper limit of 99.5 mol%.
• a resin composition such as an aqueous solution can be produced by setting the amount within the above range.
• a more preferable lower limit of the degree of saponification is 60 mol%, a more preferable lower limit is 70 mol%, a particularly preferable lower limit is 80 mol%, and a more preferable upper limit is 99 mol%.
• a more preferable upper limit is 95 mol%, and a particularly preferable upper limit is 90 mol%.
• the degree of saponification is measured according to JIS K6726.
• the degree of saponification indicates the average ratio of units actually saponified to vinyl alcohol units among units converted to vinyl alcohol units by saponification. From the viewpoint of the ease of forming an aqueous solution (resin composition) and the storage stability of the aqueous solution (resin composition), the degree of saponification of the polyvinyl alcohol resin is not a highly saponified product exceeding 98 mol%, but 98 mol% or less. A partially saponified product of 90 mol % or less is particularly preferable. When the degree of saponification is not too high, the water solubility is improved and an aqueous solution having an appropriate concentration can be prepared, thereby facilitating the formation of a protective film.
• the degree of polymerization of the polyvinyl alcohol resin is not particularly limited, the preferred lower limit is 100 and the preferred upper limit is 2,500. A more preferable lower limit is 200, and a more preferable upper limit is 1800. A more preferable lower limit is 250, a more preferable upper limit is 1300, a particularly preferable lower limit is 300, and a particularly preferable upper limit is 1000. Within the above range, both film strength and film formability can be achieved at high levels. In addition, the said degree of polymerization is measured based on JISK6726.
• the degree of polymerization When the degree of polymerization is not too high, the water solubility is improved, and a protective film-forming resin composition having an appropriate concentration and viscosity can be produced, which facilitates the formation of a protective film by spraying or a coater. If the degree of polymerization is not too low, it is possible to improve the mechanical strength of the protective film to be produced while appropriately controlling the concentration and viscosity, and to facilitate peeling and removal by making the adhesion moderate. can.
• the polyvinyl alcohol resin may be a mixture of two or more resins having different saponification degrees, polymerization degrees, etc., or may be a mixture of modified and unmodified resins.
• the polyvinyl alcohol resin can be obtained by polymerizing a vinyl ester to obtain a polymer and then saponifying, ie, hydrolyzing the polymer according to a conventionally known method.
• Alkali or acids are generally used for saponification. It is preferable to use an alkali for saponification.
• As said polyvinyl alcohol only 1 type may be used and 2 or more types may be used together.
• vinyl ester examples include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate and vinyl benzoate.
• the polymer obtained by polymerizing the above vinyl ester is preferably polyvinyl ester because the degree of saponification can be easily controlled within a suitable range.
• the method for polymerizing the vinyl ester is not particularly limited.
• Examples of this polymerization method include a solution polymerization method, a bulk polymerization method and a suspension polymerization method.
• polymerization catalyst used for polymerizing the vinyl ester examples include 2-ethylhexylperoxydicarbonate ("TrigonoxEHP" manufactured by Tianjin McEIT), 2,2'-azobisisobutyronitrile (AIBN), t-butyl peroxyneodecanoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-n-propylperoxydicarbonate, di-n-butylperoxydicarbonate, di-cetylperoxydicarbonate and di-s-butylperoxy A dicarbonate etc. are mentioned. Only one kind of the polymerization catalyst may be used, or two or more kinds thereof may be used in combination.
• the polyvinyl alcohol resin includes a modified polyvinyl alcohol resin.
• the modified polyvinyl alcohol resin may be a copolymer of the vinyl ester and other monomers, or may be a modified polyvinyl alcohol resin.
• Examples of the modified polyvinyl alcohol resin include acetoacetyl-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, and silicon atom-modified polyvinyl alcohol. denatured polyvinyl alcohol, or a graft polymer of a copolymer of polyvinyl alcohol and (acrylamide, vinylpyrrolidone, acrylonitrile).
• Examples of the above-mentioned other monomers, that is, comonomers to be copolymerized include olefins, (meth)acrylic acid and its salts, (meth)acrylic acid esters, (meth)acrylamide derivatives, N-vinylamides, vinyl ethers, nitriles, vinyl halides, allyl compounds, maleic acid and its salts, maleic acid esters, itaconic acid and its salts, itaconic acid esters, vinylsilyl compounds, polyvinylpyrrolidone, and isopropenyl acetate. Only one kind of the other monomer may be used, or two or more kinds thereof may be used in combination.
• Examples of the olefins include ethylene, propylene, 1-butene and isobutene.
• the (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, and n-(meth)acrylate. butyl, and 2-ethylhexyl (meth)acrylate.
• Examples of the (meth)acrylamide derivatives include acrylamide, n-methylacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, and (meth)acrylamidopropanesulfonic acid and salts thereof.
• N-vinylamides examples include N-vinylpyrrolidone.
• vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether and n-butyl vinyl ether.
• nitriles include (meth)acrylonitrile.
• vinyl halides include vinyl chloride and vinylidene chloride.
• allyl compound include allyl acetate and allyl chloride.
• vinylsilyl compound examples include vinyltrimethoxysilane.
• the preferred upper limit of the modified amount (percentage of modified structural units) in the modified polyvinyl alcohol resin is 25 mol%, the more preferred upper limit is 20 mol%, the even more preferred upper limit is 15 mol%, the even more preferred upper limit is 10 mol%, especially A preferred upper limit is 5 mol %, a preferred lower limit is 1 mol %, and a more preferred lower limit is 2 mol %.
• the content of the polyvinyl alcohol resin in the protective film-forming resin composition of the present invention is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 3% by weight or more, and even more preferably 5% by weight.
• % or more particularly preferably 8 wt% or more, particularly more preferably 10 wt% or more, preferably 50 wt% or less, more preferably 40 wt% or less, even more preferably 30 wt% or less, even more preferably is 25% by weight or less, particularly preferably 22.5% by weight or less, and particularly preferably 20.0% by weight or less.
• the protective film-forming resin composition of the present invention contains at least one selected from the group consisting of a plasticizer and water. In the present invention, it is particularly preferable to contain water, and to contain both a plasticizer and water.
• the protective film-forming resin composition of the present invention can improve the durability of the protective film by containing a plasticizer. Further, by including the above plasticizer, the solubility of the protective film in water and the releasability from the substrate can be improved.
• the plasticizer is not particularly limited as long as it is generally used as a plasticizer for polyvinyl alcohol, and examples thereof include polyhydric alcohols, polyethers, phenol derivatives, amide compounds and the like. Compounds obtained by adding ethylene oxide to polyhydric alcohols can also be mentioned. These may be used alone or in combination of two or more.
• the polyhydric alcohol examples include glycerin, diglycerin, diethylene glycol, trimethylolpropane, triethylene glycol, dipropylene glycol, propylene glycol and the like.
• the polyether examples include polyethylene glycol and polypropylene glycol.
• the phenol derivative examples include bisphenol A, bisphenol S, and the like.
• the amide compound examples include N-methylpyrrolidone.
• the plasticizer preferably contains 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.
• the plasticizer has a solubility parameter (SP value) hydrogen bond component ⁇ h of 8.0 (MPa 1/2 ) or more and 18 (MPa 1/2 ) or less. and more preferably 9.0 (MPa 1/2 ) or more and 17 (MPa 1/2 ) or less.
• SP value solubility parameter
• the content of the plasticizer is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, still more preferably 1.0% by weight or more, and even more preferably 1.0% by weight or more.
• the resin composition for forming a protective film of the present invention contains preferably 0.2 parts by weight or more, more preferably 1.0 parts by weight or more, still more preferably 2.0 parts by weight or more of the plasticizer with respect to 100 parts by weight of polyvinyl alcohol resin. 0 parts by weight or more, still more preferably 3.0 parts by weight or more, particularly preferably 6.0 parts by weight or more, particularly more preferably 10.0 parts by weight or more, preferably 50000 parts by weight or less, more preferably 4000 parts by weight It is preferably not more than 1167 parts by weight, more preferably not more than 600 parts by weight, particularly preferably not more than 344 parts by weight, and most preferably not more than 200 parts by weight. When the content of the plasticizer is within the above range, toughness can be imparted to the protective film.
• the water is not particularly limited, and examples thereof include ion-exchanged water, pure water, and the like. These may be used alone or in combination of two or more.
• the protective film-forming resin composition of the present invention preferably has a water content of 10 to 99.9% by weight.
• a more preferable lower limit of the water content is 20% by weight, and a more preferable upper limit is 99.0% by weight.
• a more preferable lower limit is 35.0% by weight, a more preferable upper limit is 97.0% by weight, a still more preferable lower limit is 45.0% by weight, a still more preferable upper limit is 95.0% by weight, and a particularly preferable lower limit is 52% by weight.
• a particularly preferred upper limit is 92.0% by weight
• a particularly more preferred lower limit is 60.0% by weight
• a particularly more preferred upper limit is 90.0% by weight.
• the total content of the components contained in the protective film-forming aqueous solution is 100% by weight.
• the resin composition for forming a protective film of the present invention contains preferably 20 parts by weight or more, more preferably 50 parts by weight or more, still more preferably 116 parts by weight or more of the above water with respect to 100 parts by weight of the polyvinyl alcohol resin. It is preferably 180 parts by weight or more, particularly preferably 233 parts by weight or more, particularly preferably 300 parts by weight or more, preferably 99900 parts by weight or less, more preferably 9900 parts by weight or less, and still more preferably 3233 parts by weight or less. Further, it is preferably 1900 parts by weight or less, particularly preferably 1150 parts by weight or less, and particularly preferably 900 parts by weight or less. When the content of the water is within the above range, stringiness can be suppressed during application to the base material surface, and uniform application can be facilitated.
• additives may be added to the protective film-forming resin composition of the present invention as long as the effects of the present invention are not impaired.
• additives include surfactants, antioxidants, anti-aging agents, ultraviolet absorbers, titanium coupling agents, leveling agents, thixotropic agents, anti-skinning agents, thickeners, diluents, and reactive diluents. , cross-linking agents, fillers, pigments (pigments, dyes), preservatives, antifungal agents, and the like.
• the protective film-forming resin composition of the present invention preferably further contains an antifungal agent.
• antifungal agents examples include alcohol antifungal agents, aldehyde antifungal agents, thiazoline antifungal agents, imidazole antifungal agents, ester antifungal agents, chlorine antifungal agents, and peroxide antifungal agents.
• Antifungal agent carboxylic acid antifungal agent, carbamate antifungal agent, sulfamide antifungal agent, quaternary ammonium salt antifungal agent, pyridine antifungal agent, phenol antifungal agent, iodine antifungal agent, triazole system antifungal agents and the like.
• the protective film-forming resin composition of the present invention preferably has a viscosity of 1 mPa ⁇ s or more and 10 Pa ⁇ s or less when measured with a rotary viscometer according to JIS K7117-1.
• the viscosity is more preferably 10 mPa s or more and 8 Pa s or less, still more preferably 20 mPa or more and 6 Pa s or less, even more preferably 50 mPa or more and 4 Pa s or less, and 100 mPa or more and 3 Pa s or less.
• the following are particularly preferred.
• the viscosity is preferably 1 mPa ⁇ s or more and 3 Pa ⁇ s or less.
• a more preferable lower limit of the viscosity is 10 mPa ⁇ s, a more preferable lower limit is 20 mPa ⁇ s, a still more preferable lower limit is 50 mPa ⁇ s, a more preferable upper limit is 1.8 Pa ⁇ s, and a further preferable upper limit is 1.2 Pa ⁇ s.
• a still more preferable upper limit is 0.5 Pa ⁇ s.
• the viscosity is preferably 100 mP ⁇ s or more and 10 Pa ⁇ s or less.
• a more preferable lower limit of the viscosity is 200 mPa s, a more preferable lower limit is 400 mPa s, a still more preferable lower limit is 800 mPa s, a more preferable upper limit is 8 Pa s, a further preferable upper limit is 6 Pa s, and a further more preferable upper limit. is 4 Pa ⁇ s.
• a protective film having a desired thickness can be easily formed with a uniform thickness when applying with a roll coater.
• the said viscosity is measured at 23 degreeC.
• the rotational viscometer for example, TVC-10 (manufactured by Toki Sangyo Co., Ltd.) can be used.
• the protective film-forming resin composition of the present invention preferably has a contact angle with a glass substrate of 10° or more and 75° or less at a temperature of 23° C. and a humidity of 60% RH.
• a contact angle with a glass substrate of 10° or more and 75° or less at a temperature of 23° C. and a humidity of 60% RH.
• a more preferable range of the contact angle has a more preferable lower limit of 20°, a more preferable lower limit of 25°, a still more preferable lower limit of 30°, a particularly preferable lower limit of 35°, and a more preferable upper limit of 70°.
• a more preferred upper limit is 66°, a still more preferred upper limit is 63°, and a particularly preferred upper limit is 61°.
• the contact angle can be measured by a contact angle meter (for example, DMo-502 manufactured by Kyowa Interface Science Co., Ltd., analysis software: FAMAS).
• a 0.5 mm glass substrate (TEMPAX) can be used as the contact angle measurement substrate, and more specifically, a glass substrate (TEMPAX Float manufactured by SCHOTT) can be used.
• the ⁇ /2 method (A half-angle method) can be used as a measuring method.
• the method for producing the protective film-forming resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing a polyvinyl alcohol resin, a plasticizer and water by a known method.
• the protective film of the present invention comprises the protective film-forming resin composition of the present invention. That is, the protective film of the present invention contains a polyvinyl alcohol resin and, if necessary, a plasticizer, and may contain water. By using such a protective film as a film for the base material, it is possible to prevent adhesion of foreign substances originating from the base material in the manufacturing line and the transportation line of the base material.
• the protective film of the present invention can be obtained, for example, by applying the protective film-forming resin composition to a substrate and drying by heating to remove part or all of the water.
• the protective film of the present invention may be a single layer or may have a plurality of layers.
• spray coating may be performed continuously before the drying process, and there are also protective films that integrate the interface between layers. produced.
• the composition on the substrate side, which is the interface between the substrate and the protective coating, and the composition on the side opposite to the substrate, which is the interface between the protective coating and air are different. It also includes cases where the interface between layers is not clear, such as in a continuous tilted structure.
• the viscosity of the first protective film-forming resin composition that contacts the substrate surface, and the formation of the second protective film for forming a further film on the layer is preferably 0.1 to 3,000, more preferably 0.1 to 3,000. 2 or more and 1500 or less are preferable, more preferably 0.4 or more and 1000 or less, still more preferably 0.6 or more and 500 or less, particularly preferably 0.8 or more and 250 or less, particularly preferably 1.0 or more and 150 or less .
• the protective film formed in the present invention preferably has a surface roughness Sa (arithmetic mean height according to ISO 25178) of 0.1 ⁇ m or more on the main surface opposite to the substrate.
• a surface roughness Sa (arithmetic mean height according to ISO 25178) of 0.1 ⁇ m or more on the main surface opposite to the substrate.
• the surface roughness Sa is more preferably 0.2 ⁇ m or more, still more preferably 0.4 ⁇ m or more, still more preferably 0.8 ⁇ m or more, particularly preferably 1.5 ⁇ m or more, and particularly preferably 2.0 ⁇ m or more.
• the protective film formed in the present invention preferably has a surface roughness Sz (maximum height according to ISO 25178) of 10 ⁇ m or more on the main surface opposite to the substrate.
• Sz maximum height according to ISO 25178
• the upper limit is not particularly limited, 300 ⁇ m is a substantial upper limit. Within the above range, self-adhesion between protective films and adhesion to other substrates can be reduced.
• the surface roughness Sz is more preferably 20 ⁇ m or more, still more preferably 30 ⁇ m or more, still more preferably 40 ⁇ m or more, particularly preferably 50 ⁇ m or more, and particularly preferably 60 ⁇ m or more.
• the protective film formed in the present invention preferably has a surface roughness Sdr (maximum height according to ISO 25178) of 0.1 or more on the main surface opposite to the substrate.
• Sdr maximum height according to ISO 25178
• the upper limit is not particularly limited, 30 is a substantial upper limit. Within the above range, it is possible to protect the substrate from surface scratches applied to the substrate and damage due to pressure applied to the substrate, and to enhance the thermal insulation of the substrate.
• the 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, and particularly more preferably 0.9 or more. .
• the surface roughness Sa, Sz and Sdr are 1 mm ⁇ 1 mm with a laser microscope (eg, morphological analysis laser microscope, VK-X1050, manufactured by Keyence Corporation) on the main surface opposite to the substrate of the protective film produced. is measured and calculated according to ISO 25178. This was randomly measured at 10 locations, and the average value was used as each value.
• a laser microscope eg, morphological analysis laser microscope, VK-X1050, manufactured by Keyence Corporation
• the protective film formed in the present invention preferably has a surface roughness Sa (arithmetic mean height according to ISO 25178) of 0.01 ⁇ m or more on the main surface on the substrate side.
• a surface roughness Sa (arithmetic mean height according to ISO 25178) of 0.01 ⁇ m or more on the main surface on the substrate side.
• the surface roughness Sa is more preferably 0.1 ⁇ m or more, still more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more, particularly preferably 0.4 ⁇ m or more, and particularly preferably 0.5 ⁇ m or more. .
• the protective film formed in the present invention preferably has a surface roughness Sz (maximum height according to ISO 25178) of 8 ⁇ m or more on the main surface on the substrate side.
• Sz maximum height according to ISO 25178
• the upper limit is not particularly limited, 240 ⁇ m is the substantial upper limit.
• the surface roughness Sz is more preferably 16 ⁇ m or more, still more preferably 24 ⁇ m or more, even more preferably 32 ⁇ m or more, particularly preferably 40 ⁇ m or more, and particularly preferably 48 ⁇ m or more.
• the protective film formed in the present invention preferably has a surface roughness Sdr (maximum height according to ISO 25178) of 0.05 or more on the main surface on the substrate side.
• Sdr maximum height according to ISO 25178
• 15 is a substantial upper limit. Within the above range, it is possible to protect the substrate from surface scratches applied to the substrate and damage due to pressure applied to the substrate, and to enhance the thermal insulation of the substrate.
• the 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, and particularly preferably 0.5 or more. .
• the surface roughness Sa, Sz and Sdr is a laser microscope (e.g., morphological analysis laser microscope, VK-X1050, manufactured by Keyence Corporation) on the main surface of the substrate side of the prepared protective film, in the range of 1 mm ⁇ 1 mm. is measured and calculated according to ISO 25178. This was randomly measured at 10 locations, and the average value was used as each value.
• a laser microscope e.g., morphological analysis laser microscope, VK-X1050, manufactured by Keyence Corporation
• the average cell diameter preferably has a lower limit of 0.05 ⁇ m and a preferred upper limit of 280 ⁇ m. When the average cell diameter is within this range, it is possible to enhance the protection of the substrate surface from scratches and the like.
• a more preferable lower limit of the average cell diameter is 0.5 ⁇ m, and a more preferable upper limit thereof is 225 ⁇ m.
• a more preferable lower limit is 1.0 ⁇ m
• a further preferable upper limit is 180 ⁇ m
• a still more preferable lower limit is 1.5 ⁇ m
• a still more preferable upper limit is 135 ⁇ m
• a particularly preferable lower limit is 2.0 ⁇ m
• a particularly preferable upper limit is 108 ⁇ m
• a particularly more preferable lower limit is 2.5 ⁇ m
• a particularly preferable upper limit is 90 ⁇ m.
• the average bubble diameter is obtained by observing the bubble wall portion and the void portion from the cross-sectional observation photograph of the bubble with a laser microscope (eg, morphological analysis laser microscope, VK-X1050, manufactured by Keyence Corporation), and determining the size of the void portion. It can be measured by any measuring method.
• a laser microscope eg, morphological analysis laser microscope, VK-X1050, manufactured by Keyence Corporation
• the protective film has a preferable lower limit of density of 0.1 g/cm 3 and a preferable upper limit of density of 1.3 g/cm 3 .
• a more preferable lower limit is 0.15 g/cm 3
• a still more preferable lower limit is 0.2 g/cm 3
• a still more preferable lower limit is 0.25 g/cm 3
• a particularly preferable lower limit is 0.3 g/cm 3
• a more preferred upper limit is 1.0 g/cm 3
• a still more preferred upper limit is 0.85 g/cm 3
• a particularly preferred upper limit is 0.7 g/cm 3 .
• the density can be calculated by, for example, determining the volume by observation with a laser microscope or the like, weighing the weight, and dividing the obtained weight by the volume.
• a preferred lower limit of the thickness of the protective film is 1.0 ⁇ m, and a preferred upper limit is 300 ⁇ m. If the thickness of the foam is within the above range, the protective film can be peeled off or the foam can be water-soluble. A more preferable lower limit to the thickness of the multilayer coating is 2.0 ⁇ m, and a more preferable upper limit is 250 ⁇ m.
• a more preferable lower limit is 4.0 ⁇ m, a more preferable upper limit is 200 ⁇ m, a still more preferable lower limit is 6.0 ⁇ m, a still more preferable upper limit is 150 ⁇ m, a particularly preferable lower limit is 8.0 ⁇ m, and a particularly preferable upper limit is 120 ⁇ m, A particularly more preferable lower limit is 10.0 ⁇ m, and a particularly more preferable upper limit is 100 ⁇ m.
• the thickness of the protective film can be measured by a method conforming to JIS K6783 using a constant pressure thickness gauge (eg, PG-02J manufactured by Techclock).
• the content of the polyvinyl alcohol resin in the protective film is preferably 1% by weight or more, more preferably 4% by weight or more, still more preferably 8% by weight or more, and preferably 100% by weight or less, more preferably 90% by weight. 85% by weight or less, more preferably 85% by weight or less.
• the content of the plasticizer in the protective film is preferably 0% by weight or more, more preferably 1% by weight or more, still more preferably 3% by weight or more, and even more preferably 5% by weight or more.
• the content of the polyvinyl alcohol resin in the protective film is at least the above lower limit, the protective film can be easily dried during formation, and the handleability of the laminate can be improved.
• the content of the polyvinyl alcohol resin in the protective film is equal to or less than the above upper limit, uniform film formation can be facilitated.
• the contents of the polyvinyl alcohol resin and the plasticizer in the protective film are within the above ranges, the adhesiveness, protective properties, and releasability can be further improved.
• the laminate of the invention has the protective coating of the invention and a substrate. Moreover, in the laminate of the present invention, it is preferable that the protective film further has a plasticizer layer on the substrate side. In this case, the plasticizer layer is provided between the protective film and the substrate. In the present invention, the plasticizer layer may have no specific thickness as long as it prevents direct bonding between the resin component in the protective film and the substrate, and may be a monomolecular film. good. By having such a plasticizer layer, the protective film can be easily peeled off.
• the plasticizer layer may be a single layer or multiple layers. In the present specification, the protective film alone or the protective film and the plasticizer layer together are also referred to as the glass film. Such a glass film may be generically referred to as a protective film.
• the plasticizer layer does not contain a polyvinyl alcohol resin, or the polyvinyl alcohol resin content in the plasticizer layer is is preferably less than the polyvinyl alcohol resin content of
• This plasticizer layer is bonded to the protective film at the interface, and is peeled off as a single unit when the protective film is peeled off.
• the content of the polyvinyl alcohol resin in the plasticizer layer is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and still more preferably 0.3% by weight. % by weight or more, more preferably 0.5% by weight or more, particularly preferably 0.7% by weight or more, particularly preferably 1.0% by weight or more, and preferably 87% by weight or less , more preferably 83% by weight or less, still more preferably 80% by weight or less, still more preferably 77% by weight or less, particularly preferably 74% by weight or less, and even more preferably 71.5% by weight or less.
• the content of the plasticizer in the plasticizer layer is preferably 13.0% by weight or more, more preferably 16.5% by weight or more, still more preferably 20.0% by weight or more, and even more preferably 23% by weight.
• the peelability can be further improved while maintaining high protective properties. Since the plasticizer layer cannot be separated from the protective film, the contents of the polyvinyl alcohol resin and the plasticizer in the plasticizer layer are calculated values.
• the preferred lower limit of the thickness of the plasticizer layer is 0.001 ⁇ m, more preferred lower limit is 0.005 ⁇ m, still more preferred lower limit is 0.01 ⁇ m, still more preferred lower limit is 0.05 ⁇ m, and particularly preferred lower limit is 0.1 ⁇ m.
• a more preferred lower limit is 0.5 ⁇ m, a more preferred upper limit is 50 ⁇ m, a more preferred upper limit is 40 ⁇ m, a still more preferred upper limit is 30 ⁇ m, a still more preferred upper limit is 20 ⁇ m, a particularly preferred upper limit is 15 ⁇ m, and a particularly more preferred upper limit is 10 ⁇ m. If the thickness of the plasticizer layer is within the above range, the protective film can be easily peeled off from the substrate.
• the laminate of the invention may have further layers in addition to the substrate, protective coating and plasticizer layer.
• Another layer may be a layer having the same composition as the protective coating or plasticizer layer.
• the laminate of the present invention preferably has a peel strength between the protective coating and the substrate of 2.5 N/25 mm or less in a 180° peel strength test.
• the peel strength is 2.5 N/25 mm or less, the protective film can be easily peeled off from the substrate.
• a preferred upper limit of the peel strength is 2.0 N/25 mm, a more preferred upper limit is 1.5 N/25 mm, a still more preferred upper limit is 1.2 N/25 mm, a still more preferred upper limit is 1.0 N/25 mm, and a particularly preferred upper limit is 0.5 N/25 mm. It is 8N/25mm.
• a preferable lower limit is not particularly limited, but is, for example, 0.01 N/25 mm.
• the 180° peel strength test is preferably within the above range.
• the 180° peel strength can be measured by a method according to ISO29862:2007 or JIS Z 0237:2009.
• the peel strength between the protective film and the substrate of the laminate of the present invention can be measured by the 90° peel strength test as well as the 180° peel strength test.
• the 90° peel strength can be measured by a method according to ISO29862:2007 or JISZ0237:2009.
• the method for producing the protective film and the laminate of the present invention is not particularly limited, but the step of molding the substrate and the formation of the protective film by applying the resin composition for forming the protective film of the present invention to the molded substrate.
• a manufacturing method having a step of carrying out is preferable.
• a known method can be used as the step of molding the substrate.
• the base material is glass
• methods for molding the glass include a slot down draw method, a fusion method, a float method, and the like. Among them, it is preferable to use the fusion method.
• the above-mentioned fusion method introduces molten glass raw materials into a long and narrow gutter-shaped spout, overflows on both sides along the longitudinal direction and flows down, and the molten glass that has flowed down is reunited under the gutter.
• the glass is made by dropping the glass as it is and slowly cooling it to solidify it.
• the step of molding the base material is performed even when a base material such as a commercially available glass, plastic base material, or metal base material is used.
• Examples of methods for applying the protective film-forming resin composition of the present invention include roll coating, dip coating, spin coating, fountain coating, and spray coating. Among them, application by spraying is preferable.
• the state of the substrate is not particularly limited, and includes, for example, the state before the glass is molded and solidified, as well as the state after the glass is solidified. In addition, the substrate may be polished or surface-treated as necessary.
• the protective film-forming resin composition of the present invention is spray-coated onto a hot substrate, the resulting protective film becomes foamed.
• the resin composition for forming a protective film of the present invention is applied to a base material at a low temperature to normal temperature by a roll coater or the like, the obtained protective film is smooth without foaming.
• the temperature of the substrate when applying the protective film-forming resin composition of the present invention is preferably 0° C. or higher and 400° C. or lower. Within the above range, a protective film can be formed by applying to a substrate at a high temperature, and a protective film can be formed by heating and drying after application at a low temperature.
• the protective film-forming resin composition of the present invention is preferably used to form a protective film by applying it to a substrate having the temperature described above and drying it by heating.
• a more preferable lower limit of the above temperature is 15°C
• a still more preferable lower limit is 40°C
• a still more preferable lower limit is 75°C
• a particularly preferable lower limit is 100°C, in order to produce a protective film having the desired surface roughness.
• a more preferred lower limit is 150°C
• a more preferred upper limit is 380°C
• a still more preferred upper limit is 360°C
• a still more preferred upper limit is 340°C
• a particularly preferred upper limit is 320°C
• a particularly more preferred upper limit is 300°C.
• the substrate temperature is 400° C. or lower
• foam breakage can be prevented, and adhesion of cut cullet to the surface can be suppressed.
• the substrate temperature is 0° C. or higher, the protective film can be easily formed without post-heating.
• a method for adjusting the temperature of the base material for example, in the case of molding glass using the fusion method, a method of coating in the step of slowly cooling the molten glass can be mentioned.
• the method of heating glass is mentioned.
• the above temperature means the temperature of the substrate surface at the time of application.
• the step of applying the protective film-forming resin composition of the present invention may be performed in multiple steps. Moreover, when performing the said application
• a protective film-forming resin composition other than the present invention may be used to form a layer (inner layer) in contact with glass, and a protective film-forming resin composition of the present invention may be used for the other layer (outer layer).
• a protective film-forming resin composition other than the present invention that does not contain a plasticizer is used, the anti-blocking property of the plasticizer can be further improved.
• the said coating process may be performed only on one side of a base material, and may be performed on both sides.
• the layer (inner layer) in contact with the glass if a protective film-forming resin composition other than the present invention is used and the other layer (outer layer) is the protective film-forming resin composition of the present invention, peeling is particularly easy. Therefore, the protective film can be easily removed in the washing process for removing the protective film from the glass surface.
• the drying process is performed after performing the coating process multiple times, a multilayer protective film with a clear interface may be formed, but after performing the coating process multiple times, the drying process is performed. If not, the layered product reflects the respective coating compositions, but the interface may not be clear, resulting in a tilted structure that cannot be separated. Formation of such a gradient structure film and the film are also within the scope of the present invention.
• a step of drying may be performed. Thereby, a protective film can be formed regardless of the substrate temperature.
• the drying temperature in the secondary drying is preferably 50°C or higher and 450°C or lower.
• the protective film-forming resin composition of the present invention can be used as a protective film for glass, plastic substrates (organic polymer substrates), metal substrates, and the like. Moreover, even when a printed wiring board (PWB) is used as a base material, it can be used as a PWB protective material, particularly as an exposure protective material. In this case, since Na has a bad effect on the Cu wiring, it is preferable to remove Na from the polyvinyl alcohol resin as much as possible. In the case of the application using any base material, it is not incorporated into the final product, but can be used particularly preferably as a protective material between the base material manufacturing processes and as a temporary protective material on the premise of removal. I can.
• the base material when PWB is used as the base material, it is possible to prevent adsorption of foreign matter due to static electricity by dissolving it in water without peeling it off, and furthermore, it is possible to eliminate oxygen inhibition in UV curing, which cannot be completely removed by film lamination. Since the present invention can remove the protective film by dissolving it in water without peeling off, it can be suitably used as a protective material for ultra-thin glass that is extremely fragile.
• the present invention provides a protective film-forming resin composition, a protective film, and a laminate capable of forming an easily removable protective film to which foreign substances originating from the base material are less likely to adhere in production lines and transportation lines. can do.
• Example 1 Preparation of protective film-forming aqueous solution [resin composition for protective film-forming]
• Unmodified polyvinyl alcohol (SELVOL 203 manufactured by Sekisui Chemical Co., Ltd. degree of polymerization 300, degree of saponification 88 mol%) 100 parts by weight, 30 parts by weight of diglycerin as a plasticizer are dissolved in 370 parts by weight of water and mixed to obtain a resin content
• An aqueous solution for forming a protective film having a plasticizer content of 20% by weight and a plasticizer content of 6% by weight was prepared.
• a glass substrate (Eagle XG 150 mm ⁇ 150 mm ⁇ 0.5 mm, manufactured by Corning Incorporated) was heated on a hot plate so that the central portion of the glass substrate reached 300°C.
• the heated glass substrate is moved to a spray table, and when the central portion of the glass reaches 250° C., the obtained aqueous solution for forming a protective film is sprayed onto the glass substrate once, and then placed in a batch-type hot air circulation drying oven (150 °C setting) for 60 seconds to obtain a laminate having a glass film formed on the surface of the glass substrate.
• AGB50 (Asahi Sunac Co., Ltd., caliber 1.0mm ⁇ , cap HN400A) was used as the spray gun for applying the aqueous solution for forming the protective film, and pressure feed pump PT-10DW (manufactured by Anest Iwata Co., Ltd.) and a coating robot were used as the paint supply equipment.
• EPX-1250 DX100 (manufactured by Yaskawa Electric Co., Ltd.) was used.
• spray coating was performed using the same spray gun, coating supply device, and coating robot as described above.
• the amount of discharge from the spray gun when spraying the aqueous solution for forming a protective film was 20 g/30 seconds, and the spray conditions were as follows: the pressure of the pressure feed pump was 2.0 MPa, the liquid pressure was 0.2 MPa, and the pressure of the spray gun was 2.0 MPa. The air pressure was set to 0.2 MPa, and the coating speed of the coating robot was set to 50 mm/sec.
• Example 2 Instead of 100 parts by weight of unmodified polyvinyl alcohol (SELVOL 203 manufactured by Sekisui Chemical Co., Ltd. degree of polymerization 300, degree of saponification 88 mol%), unmodified polyvinyl alcohol (SELVOL 205 manufactured by Sekisui Chemical Co., Ltd. degree of polymerization 500, degree of saponification 88 mol %) and 30 parts by weight of diglycerin as a plasticizer are dissolved and mixed in 537 parts by weight of water to form a protective film with a resin content of 15% by weight and a plasticizer content of 4.5% by weight. An aqueous solution was prepared, and in the same manner as in Example 1, a laminate having a protective film-forming aqueous solution and a glass film formed thereon was prepared.
• SELVOL 203 unmodified polyvinyl alcohol
• SELVOL 205 manufactured by Sekisui Chemical Co., Ltd. degree of polymerization 500, degree of saponification 88 mol
• Example 3 In place of 100 parts by weight of unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd. SELVOL 203 polymerization degree 300, saponification degree 88 mol%), unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd. SELVOL 103 polymerization degree 300, saponification 10 parts by weight of diglycerin as a plasticizer is dissolved in 890 parts by weight of water and mixed to form a protective film with a resin content of 10% by weight and a plasticizer content of 1% by weight. In the same manner as in Example 1, an aqueous solution for forming a protective film was produced, and a laminate having a glass film formed thereon was produced.
• Example 4 Preparation of protective film [glass film]
• a glass substrate (Eagle XG 150 mm ⁇ 150 mm ⁇ 0.5 mm, manufactured by Corning Incorporated) was heated on a hot plate so that the central portion of the glass substrate reached 300°C.
• the heated glass substrate is moved to a spray table, and when the central portion of the glass reaches 250° C., the aqueous solution for forming a protective film obtained in Example 1 is spray-coated once onto the glass substrate, and furthermore, After spraying the aqueous solution for forming a protective film obtained in Example 3 once, it is dried for 60 seconds in a batch-type hot air circulation drying oven (set at 150 ° C.), and two layers [inner layer, Outer Layer] A laminate having a glass film formed thereon was obtained.
• AGB50 (Asahi Sunac Co., Ltd., caliber 1.0mm ⁇ , cap HN400A) was used as the spray gun for applying the aqueous solution for forming the protective film
• pressure feed pump PT-10DW manufactured by Anest Iwata Co., Ltd.
• EPX-1250 DX100 manufactured by Yaskawa Electric Co., Ltd.
• the discharge amount from the spray gun when spraying the protective film forming aqueous solution [for inner layer] was set to 10 g/30 seconds, and the discharge amount of the protective film forming aqueous solution [for outer layer] was set to 10 g/30 seconds.
• the spraying conditions were as follows: the pressure of the pumping pump was 2.0 MPa, the liquid pressure was 0.2 MPa, the air pressure of the spray gun was 0.2 MPa, and the coating speed of the coating robot was 50 mm/sec.
• Example 5 (Preparation of aqueous solution for forming protective film) Formation of a protective film in the same manner as in Example 1 except that 100 parts by weight of unmodified polyvinyl alcohol (SELVOL 203 manufactured by Sekisui Chemical Co., Ltd., polymerization degree 300, saponification degree 88 mol%) was used and no plasticizer was added. An aqueous solution was prepared.
• unmodified polyvinyl alcohol SELVOL 203 manufactured by Sekisui Chemical Co., Ltd., polymerization degree 300, saponification degree 88 mol%
• AGB50 (Asahi Sunac Co., Ltd., caliber 1.0mm ⁇ , cap HN400A) was used as the spray gun for applying the aqueous solution for forming the protective film, and pressure feed pump PT-10DW (manufactured by Anest Iwata Co., Ltd.) and a coating robot were used as the paint supply equipment.
• EPX-1250 DX100 (manufactured by Yaskawa Electric Co., Ltd.) was used.
• Example 6 In place of 100 parts by weight of unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd. SELVOL 203 polymerization degree 300, saponification degree 88 mol%), unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd. SELVOL 513 polymerization degree 1300, saponification 88 mol%) was used, and the addition amount of the plasticizer, the resin content, and the plasticizer content were set as shown in Table 1. A laminate with a film formed thereon was produced.
• Example 7 A laminate having a protective film-forming aqueous solution and a glass film was produced in the same manner as in Example 6, except that no plasticizer was used.
• Example 8 In place of 100 parts by weight of unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd. SELVOL 203 degree of polymerization 300, saponification degree 88 mol%), unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd. SELVOL 518 degree of polymerization 1800, saponification 88 mol%) was used, and the addition amount of the plasticizer, the resin content, and the plasticizer content were set as shown in Table 1. A laminate with a film formed thereon was produced.
• Example 9 A laminate having a protective film-forming aqueous solution and a glass film was produced in the same manner as in Example 8, except that no plasticizer was used.
• Example 10 In place of 100 parts by weight of unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd. SELVOL 203 polymerization degree 300, saponification degree 88 mol%), unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd. SELVOL 418 polymerization degree 1800, saponification Aqueous solution for forming a protective film was prepared in the same manner as in Example 1, except that 100 parts by weight of 92.0 mol %) was used, and the amount of plasticizer added, the resin content, and the plasticizer content were set as shown in Table 1. , a laminate having a glass film formed thereon was produced.
• Example 11 A laminate having a protective film-forming aqueous solution and a glass film formed thereon was produced in the same manner as in Example 10, except that no plasticizer was used.
• Example 12 (Preparation of protective film forming aqueous solution [for inner layer, outer layer])
• 100 parts by weight of diglycerin as a plasticizer was dissolved in 1900 parts by weight of water and mixed to prepare an aqueous solution for forming a protective film [for inner layer] with a plasticizer content of 5% by weight.
• unmodified polyvinyl alcohol (SELVOL 203 manufactured by Sekisui Chemical Co., Ltd., degree of polymerization: 300, degree of saponification: 88 mol%) 100 parts by weight, 15 parts by weight of diglycerin as a plasticizer are dissolved in 385 parts by weight of water and mixed to form a resin.
• a protective film-forming aqueous solution [for outer layer] was prepared with a plasticizer content of 20% by weight and a plasticizer content of 3% by weight.
• a glass substrate (Eagle XG 150 mm ⁇ 150 mm ⁇ 0.5 mm, manufactured by Corning Incorporated) was heated on a hot plate so that the central portion of the glass substrate reached 400°C.
• the heated glass substrate was moved to a spray table, and when the central portion of the glass reached 350°C, the protective film-forming aqueous solution [for inner layer] obtained in Example 12 was sprayed once onto the glass substrate, Furthermore, the protective film forming aqueous solution [for outer layer] obtained in Example 12 was sprayed once over it, and dried in a batch type hot air circulation drying oven (set at 150 ° C.) for 60 seconds.
• a laminate was obtained in which two layers [an inner layer and an outer layer] of glass films were formed on the surface of the .
• the discharge amount from the spray gun when applying the protective film forming aqueous solution [for inner layer] is set to 8 g/30 seconds, and the discharge amount when applying the protective film forming aqueous solution [for outer layer] is set to 12 g/30 seconds. bottom.
• the spraying conditions were as follows: the pressure of the pumping pump was 2.0 MPa, the liquid pressure was 0.2 MPa, the air pressure of the spray gun was 0.2 MPa, and the coating speed of the coating robot was 50 mm/sec.
• Example 13-15 In the same manner as in Example 12 except that the amount of plasticizer in the aqueous solution for forming a protective film for the outer layer was changed as shown in Table 1, A laminate was obtained in which two layers [inner layer, outer layer] of the glass film were formed.
• Example 16 In place of 100 parts by weight of unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd. SELVOL 203 degree of polymerization 300, saponification degree 88 mol%), unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd. SELVOL 205 degree of polymerization 500, saponification In the same manner as in Example 12, except that 100 parts by weight of an aqueous solution for forming a protective film [outer layer for] was produced.
• Example 12 Two layers [inner layer, outer layer] were formed on the surface of a glass substrate (Eagle XG 150 mm ⁇ 150 mm ⁇ 0.5 mm manufactured by Corning) in the same manner as in Example 12 except that the obtained aqueous solution for forming a protective film [for outer layer] was used. A laminate having a glass film formed thereon was obtained.
• Examples 17-19 In the same manner as in Example 12 except that the amount of plasticizer in the aqueous solution for forming a protective film for the outer layer was changed as shown in Table 1, A laminate was obtained in which two layers [inner layer, outer layer] of the glass film were formed.
• Example 20 In the same manner as in Example 12, except that 18 parts by weight of glycerin was used as the plasticizer instead of 15 parts by weight of diglycerin, and the amount of plasticizer added, the resin content, and the plasticizer content were changed as shown in Table 1. , an aqueous solution for forming a protective film [for outer layer] was prepared. A laminate having a glass film formed thereon was produced in the same manner as in Example 12 except that the obtained aqueous solution for forming a protective film [for outer layer] was used.
• Example 21 Without adding unmodified polyvinyl alcohol, 100 parts by weight of glycerin as a plasticizer was dissolved in water and mixed to prepare an aqueous solution for forming a protective film [for inner layer] with a plasticizer content of 3% by weight. In place of 100 parts by weight of unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd. SELVOL 203 degree of polymerization 300, saponification degree 88 mol%), unmodified polyvinyl alcohol (Sekisui Chemical Co., Ltd.
• SELVOL 205 degree of polymerization 500 saponification 100 parts by weight of 100 parts by weight of 100 parts by weight of plasticizer (88 mol %), 18 parts by weight of glycerin was used as a plasticizer instead of 15 parts by weight of diglycerin, and the amount of plasticizer added, the resin content, and the plasticizer content were as shown in Table 1.
• An aqueous solution for forming a protective film [for outer layer] was prepared in the same manner as in Example 12, except for the above.
• a laminate having a glass film formed thereon was produced in the same manner as in Example 12 except that the obtained protective film-forming aqueous solution [for inner layer] and protective film-forming aqueous solution [for outer layer] were used.
• Example 22 (Preparation of aqueous solution for forming protective film) An aqueous solution for forming a protective film was prepared in the same manner as in Example 1 with the formulation shown in Table 1. Laminate with a glass film formed in the same manner as in Example 1 except that the obtained aqueous solution for forming a protective film was sprayed once on the glass substrate when the central part of the glass reached 350 ° C. made the body.
• Example 23 A laminated body having a protective film-forming aqueous solution and a glass film was produced in the same manner as in Example 22, except that the resin content was changed from 20% by weight to 3% by weight when producing the protective film-forming aqueous solution. .
• Example 24 Instead of 100 parts by weight of unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Co., Ltd., SELVOL 203, degree of polymerization 300, degree of saponification 88 mol%), unmodified polyvinyl alcohol (manufactured by Sekisui Chemical Co., Ltd., SELVOL 103, degree of polymerization 300, degree of saponification 98.4 mol%), and in the same manner as in Example 23 with the composition and concentration shown in Table 1, a laminate having a protective film-forming aqueous solution and a glass film formed thereon was produced.
• Example 25 WRA-M200 (manufactured by Anest Iwata Co., Ltd., diameter 0.8 mm, cap type 01) as a spray gun for applying the aqueous solution for forming a protective film, and PT-10DW (manufactured by Anest Iwata Co., Ltd.) as a pressure feed pump for the inner layer as a paint supply device.
• WRA-M200 manufactured by Anest Iwata Co., Ltd., diameter 0.8 mm, cap type 01
• PT-10DW manufactured by Anest Iwata Co., Ltd.
• PT-20DW manufactured by Anest Iwata
• EPX-1250 DX100 manufactured by Yaskawa Electric
• the spray gun when applying the aqueous solution for forming the protective film [for the inner layer] was set at 16 g/30 seconds
• the ejection amount when applying the protective film-forming aqueous solution [for outer layer] was set at 24 g/30 seconds.
• a laminate having a glass film formed thereon was produced in the same manner as in Example 18, except that the spray conditions were as follows.
• the spray conditions were as follows: the pressure of the protective film forming aqueous solution [for the inner layer] was 2.0 MPa, the discharge pressure of the FCV (float control valve) was 0.2 MPa, and the pattern pressure of the spray gun was 0.125 MPa. , the atomization pressure was set to 0.1 MPa, and the coating speed of the coating robot was set to 50 mm/sec.
• the pressure of the pressure pump for the aqueous solution for forming the protective film [for the outer layer] is 0.2 MPa
• the discharge pressure of the FCV (float control valve) is 0.5 MPa
• the pattern pressure of the spray gun is 0.175 MPa
• the atomization pressure is 0. .1 MPa
• the coating speed of the coating robot was 50 mm/sec.
• Example 26 An aqueous solution for forming a protective film and a laminate having a glass film formed thereon were produced in the same manner as in Example 2, except that the temperature of the glass substrate was 150°C.
• Example 27 A laminate having a protective film-forming aqueous solution and a glass film formed thereon was produced in the same manner as in Example 16, except that the temperature of the glass substrate was 150°C.
• Example 28 In the same manner as in Example 2, except that the resin (PVA) content was 30% by weight, the temperature of the glass substrate was 100° C., and a roll coater (slide coater manufactured by Furnace Co., Ltd.) was used instead of the spray. A laminate having a protective film-forming aqueous solution and a glass film formed thereon was produced.
• Example 29 A laminate having a protective film-forming aqueous solution and a glass film was produced in the same manner as in Example 28, except that no plasticizer was used.
• Example 30 The resin (PVA) content of the protective film forming aqueous solution [for the outer layer] is 30% by weight, the glass substrate temperature is 150 ° C., and a roll coater (manufactured by Furnace Co., Ltd., slide coater) is used instead of a spray to apply two continuous coatings.
• a roll coater manufactured by Furnace Co., Ltd., slide coater
• Example 31 A laminate having a protective film-forming aqueous solution and a glass film was produced in the same manner as in Example 30, except that no plasticizer was used.
• Example 34 Ultra-thin glass UTG (manufactured by Corning, Willow glass 150 mm ⁇ 150 mm ⁇ 50 ⁇ m) was used instead of the glass substrate (Eagle XG 150 mm ⁇ 150 mm ⁇ 0.5 mm, manufactured by Corning). A laminate having a film formed thereon was produced in the same manner as in Example 28, except that the was changed as shown in Table 1.
• Example 35 An aqueous solution for forming a protective film and a laminate with a film formed were prepared in the same manner as in Example 34, except that no plasticizer was added to the aqueous solution for protective film and the composition of the aqueous solution was changed as shown in Table 1. bottom.
• Example 36 Example 2 except that a coated steel plate (automobile simulation panel manufactured by Nippon Test Panel Co., Ltd.) was used instead of the glass substrate (Eagle XG 150 mm ⁇ 150 mm ⁇ 0.5 mm manufactured by Corning), and the substrate temperature was 20 ° C. Similarly, an aqueous solution for forming a protective film and a laminate having a film formed thereon were produced.
• a coated steel plate automobile simulation panel manufactured by Nippon Test Panel Co., Ltd.
• the glass substrate Etheral XG 150 mm ⁇ 150 mm ⁇ 0.5 mm manufactured by Corning
• Comparative example 2 As shown in Table 1, an aqueous solution for forming a protective film containing 40% by weight of a plasticizer and a laminate having a glass film formed thereon were prepared in the same manner as in Comparative Example 1 except that only diglycerin, which is a plasticizer, was prepared as an aqueous solution. made the body. The film consisted only of diglycerin, a plasticizer, and water.
• Comparative Example 3 An aqueous solution for forming a protective film with a plasticizer content of 3% by weight and a glass film were formed in the same manner as in Comparative Example 1 except that glycerin was used as the plasticizer instead of diglycerin and the aqueous solution was prepared as shown in Table 1. A laminated body was produced. The film consisted only of glycerin, a plasticizer, and water.
• Comparative Example 4 As shown in Table 1, an aqueous solution for forming a protective film containing 20% by weight of a plasticizer and a laminate in which a glass film was formed were prepared in the same manner as in Comparative Example 3, except that only glycerin, which is a plasticizer, was prepared as an aqueous solution. was made. The film consisted only of glycerin, a plasticizer, and water.
• the contact angle of the glass substrate used with deionized water was 37.5°. If the contact angle between the protective film-forming aqueous solution and the adherend is kept low, repelling is suppressed during film formation, and a uniform protective film free of pinholes and the like can be formed.
• the prepared aqueous solution for forming a protective film was dispensed into a mayonnaise bottle, covered with a lid, and cured at a temperature of 23° C. and a humidity of 60% RH for 2 days (48 hours).
• a rotational viscometer (TVC-10, manufactured by Toki Sangyo Co., Ltd.)
• the aqueous solution for forming a protective film after curing under the conditions of a temperature of 23 ° C. and a humidity of 60% RH, a method in accordance with JIS K7117-1. Viscosity evaluation was performed at By controlling the viscosity of the protective film-forming aqueous solution, the film can be easily formed.
• the viscosity When the viscosity is not too high, it is possible to obtain a good film by causing stringiness, particularly in a process such as spray film formation, and further to prevent contamination of the surroundings. When the viscosity is not too low, it is possible to prevent the foam diameter from becoming too large, impairing the homogeneity of the film, and the drying time from being too long.
• the glass film is peeled off from the obtained laminate on which the glass film is formed, and the thickness of the glass film is measured using a constant pressure thickness measuring machine (eg, PG-02J manufactured by Teclock Co., Ltd.) by a method conforming to JIS K6783. It was measured.
• a constant pressure thickness measuring machine eg, PG-02J manufactured by Teclock Co., Ltd.
• the thickness of the laminated body on which the glass film was formed was measured with the above constant pressure thickness gauge, and the value obtained by subtracting the thickness of the glass substrate previously measured by the same method was used as the thickness.
• a laser microscope morphological analysis laser microscope, VK-X1050, manufactured by Keyence Corporation
• the average thickness was taken as the thickness of the film. .
• the thickness of the film is not too thin, so that the performance as a protective film is exhibited, and the thickness of the film is not too thick, which prevents the occurrence of process incompatibility such as increased costs and long drying times. be able to.
• the surface roughness Sa, Sz, and Sdr of the main surface opposite to the base material was measured by measuring the main surface opposite to the base material (air interface side surface) of the laminated body on which the prepared glass film was formed, by laser microscope (e.g. : A morphological analysis laser microscope, VK-X1050, manufactured by Keyence Corporation) was used to measure a range of 3 mm ⁇ 3 mm.
• Each surface roughness was calculated according to ISO 25178 from the measured values obtained. This was randomly measured at 10 locations, and the average value was used as each value. The outer periphery of the measurement range was removed in a square shape with a width of 3 mm to expose the base material, which was used as a reference point.
• the surface roughnesses Sa, Sz, and Sdr of the main surface on the substrate side were obtained by peeling off the glass film from the laminated body on which the glass film was formed, and evaluating the main surface on the glass substrate side in the same manner. By controlling the surface roughness, it is possible to suppress blocking during stacking and storing or transporting the glass (laminate) with the film laminated thereon.
• the glass film of the obtained laminate was cut and cut along a plane parallel to the thickness direction with a razor blade. Then, using a digital microscope (manufactured by Keyence Corporation, product name VHX-900), a 200-fold enlarged photograph was taken, and the maximum foam diameter in the normal direction of the cut surface in the thickness direction was measured. This operation was repeated 10 times at different measurement locations, and the average value of the observed foam diameters was taken as the average bubble diameter. The diameter of each bubble was determined by the diameter of the inscribed circle having the maximum diameter when the inscribed circle inscribed in the observed bubble was drawn. The obtained foam diameter (average bubble diameter) was evaluated according to the following criteria.
• the foam diameter was 20% or more of the thickness of the glass film ⁇ : The foam diameter was 5% or more, less than 20% of the thickness of the glass film ⁇ : The foam diameter was less than 5%, 1% of the thickness of the glass film It was above ⁇ : The foam diameter was less than 1% of the thickness of the glass film
• the degree of crystallinity was measured by peeling off the glass film from the laminate, measuring the surface in close contact with the glass as the "glass interface”, and measuring the opposite surface as the "surface”. Similarly, in the case of the two-layer structure, the surface that was in close contact with the glass was measured as the "glass interface", and the opposite surface was measured as the "surface”. High: 50% or more Medium: Less than 50% 30% or more Low: Less than 30% If the degree of crystallinity is low, the surface of the film on the substrate side is plasticized, the adhesion to the substrate becomes low, and peeling and water removal become easier, and the degree of crystallinity on the air interface (surface) side of the film increases. When is high, the adhesiveness becomes low, and blocking can be suppressed when laminating the film-laminated glass during storage and transportation.
• the measurement method conformed to ISO29862:2007 or JIS Z 0237:2009.
• the adhesive tape with a base material was fixed to the jig on the upper side. Evaluation conditions were 300 mm/sec, temperature of 25° C., and humidity of 50%. If the peel strength can be set low, the protective coating can be peeled off more easily.
• the glass film was removed by three methods: 1. removal by peeling, 2. removal by washing with water, and 3. removal by washing with water after peeling (washing with water after peeling). [1. Removal by peeling]
• the obtained laminate (150 mm ⁇ 150 mm) was cut to prepare a glass sample with a glass film of 10 mm ⁇ 10 mm, and the glass film was removed by peeling. [2. Removal by washing with water] On the glass film surface of the obtained laminate (150 mm ⁇ 150 mm), steam at 85 to 90 ° C.
• the sample from which the glass film was removed by peeling was sprayed with steam at 85 to 90°C from a nozzle with a slit width of 0.1 mm at a maximum steam pressure of 0.2 MPa and 2 L/min, and then washed with warm water at 90°C. Then, normal temperature water washing was performed with a slit nozzle.
• XPS evaluation X electron spectroscopy (XPS, PHI5000 VersaProbe II, ULVAC (manufactured by Phi), and the composition and quantification of the residue on the outermost surface were performed. Measurement conditions were as follows: monochromatic AlK ⁇ (1486.6 eV) was used as a light source, photoelectron take-off angle was 45 degrees, and X-ray beam diameter was 200 ⁇ m. A glass substrate of the same type as that used in the production was subjected to "2. Removal by washing with water” and used as a reference sample. The glass substrate (manufactured by Corning, EagleXG 150 mm x 150 mm x 0.5 mm) used for the measurement itself was 2.
• the carbon atom weight was 14.0 atom % when evaluated in the same process as removal by washing with water. XPS evaluation of the glass surface was performed, and the carbon atomic weight (%) was calculated based on the carbon atomic weight (atom%) of the reference sample [(measured carbon atomic weight / carbon atomic weight of the reference sample) ⁇ 100], and the following evaluated according to the standard.
• the amount of carbon atoms (atom%) based on the reference sample is proportional to the amount of residual film that is invisible after the removal of the glass film. Show that it is easy.
• Carbon atomic weight is 150% or less ⁇ : Carbon atomic weight is more than 150% and 250% or less ⁇ : Carbon atomic weight is more than 250% and 400% or less ⁇ : Carbon atomic weight is more than 400%
• the cleaning process can be performed more easily and simply, such as by reducing the amount of detergent used. It is possible to obtain the effect of reducing the environmental impact by reducing the amount of water used, and the effect of reducing the environmental impact such as reducing the washing water.
• the brush cleaning process for removing the organic residue on the glass surface can be facilitated, and the surface damage caused by the brush cleaning can be reduced.
• the obtained two laminates (150 mm ⁇ 150 mm) are stacked so that the glass film surfaces are in close contact with each other, and 3.0 kg of a SUS plate of the same size or more is placed on it, and the environment is 25 ° C and 50% RH. It was left on the bottom for a week. After that, the two laminates were peeled off, and the breakage rate of the glass film was confirmed and evaluated according to the following criteria.
• ⁇ Damage rate of glass film is 10% or less ⁇ : Damage rate of glass film is more than 10% and 30% or less ⁇ : Damage rate of glass film is more than 30% and 50% or less ⁇ : Glass Breakage rate of the film is more than 50% In addition, if the storability is good, more glass can be laminated and temporarily stored, and the efficiency in glass production can be improved.
• silica particles (average particle size: 3 ⁇ m) were dry-sprayed onto the glass film side of the obtained laminate to adhere to the film. Next, the film was peeled off, and the presence or absence of silica particles was confirmed with an optical microscope at 5 cm square in the central portion of the 15 cm square glass and evaluated according to the following criteria.
• silica particles could be confirmed ⁇ : 10 or less silica particles could be confirmed ⁇ : 11 to 20 silica particles could be confirmed ⁇ : 21 to 50 silica particles could be confirmed ⁇ : 51 or more silica particles could be confirmed If the protective film is highly effective in removing foreign matter, the glass surface can be protected from fine glass cullets that are generated when the glass is broken during glass manufacturing or when the glass is dropped or scattered due to transportation errors. Glass cullet adhering to the glass surface is subject to quality control restrictions.
• the exfoliated coating had soil biodegradability. If it has soil biodegradability, it can be said to have environmental compatibility.
• the film that can be removed by washing with water can be completely dissolved in water, and like the film that wraps the detergent in the detergent-containing gel ball, it can be disposed of in normal sewage, so it is environmentally friendly. have a sexuality.
• ⁇ Has soil biodegradability
• ⁇ No soil biodegradability If the protective coating is biodegradable, the removed protective coating can be discarded without exacerbating the problem of waste plastics, which is increasing worldwide.
• the present invention it is possible to provide a protective film-forming resin composition, a protective film, and a laminate capable of forming a film to which foreign matter originating from the base material hardly adheres in production lines and transportation lines.

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