JP2019018153A - Method for producing coating material - Google Patents

Abstract

To provide a production method that is a method for forming a coating layer on a base material using an aqueous coating composition, which enables a high production speed and has good productivity.SOLUTION: A method for producing a coating material having at least a base material and a coating layer includes: a salt aqueous solution coating step of coating a salt aqueous solution onto at least one surface of the base material; an aqueous coating composition coating step of further coating an aqueous coating composition onto the salt aqueous solution surface; and a coating layer formation step of separating moisture from the aqueous coating composition coating layer to form a coating layer, where the aqueous coating composition contains one or more aqueous resin dispersion bodies selected from resin emulsion, a cationic dispersion resin and an anionic dispersion resin, and an amount of salt to be coated in the salt aqueous solution coating step is 0.3 to 10 g/mper surface area of the base material.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a coating material having at least a substrate and a coating layer, wherein the coating layer of the coating material is produced using an aqueous coating composition.

  Release paper has the role of protecting adhesive surfaces, sticking adhesive surfaces together and preventing sticking, and is widely used in general. The release paper is produced by providing a release layer on a substrate. The release layer is generally formed by applying a release layer forming coating composition.

  Examples of the release layer-forming coating composition include a solvent-type coating composition and an aqueous coating composition. Solvent-type coating compositions generally have the advantages of high drying speed due to the high volatility of the solvent, the ability to form a release layer at a higher speed, high production speed and excellent manufacturability. However, in recent years, there has been a demand for water-based coating compositions from the standpoints of reducing environmental impacts such as environmental pollution and safety and hygiene in manufacturing operations.

  However, since the aqueous coating composition has a lower drying speed than the solvent-based coating composition, there is a technical problem that the production speed is slow and the manufacturability is poor. Therefore, the method of forming a peeling layer using a solvent-type coating composition is still mainstream.

  A technique for forming a release layer using an aqueous coating composition has also been studied. For example, Japanese Patent Laid-Open No. 6-248244 (Patent Document 1) describes an emulsion type release agent or penetration of the release agent and the release agent into the paper layer on the surface of kraft stretched paper, kraft paper or recycled paper. The release paper for adhesive tapes which apply | coats the mixture with the viscosity modifier for controlling is disclosed. This Patent Document 1 describes that by using a viscosity modifier, release paper production using an emulsion-type release agent can be suitably performed, and productivity is improved.

JP-A-6-248244

  An object of the present invention is to solve the above-described problems of the prior art. More specifically, the present invention aims to provide a method for forming a coating layer on a substrate using an aqueous coating composition, which enables a high production rate and good manufacturability. And

In order to solve the above problems, the present invention provides the following aspects.
[1]
A method for producing a coating material having at least a substrate and a coating layer, the following steps:
A salt solution coating process for coating a salt solution on at least one surface of the substrate;
An aqueous coating composition coating step for further coating an aqueous coating composition on the surface of the aqueous salt solution coating, and a coating layer forming step for separating the water from the aqueous coating composition coating layer to form a coating layer;
Including
The aqueous coating composition includes one or more aqueous resin dispersions selected from resin emulsions, cationic dispersion resins and anionic dispersion resins, and the amount of salt applied in the salt aqueous solution coating step is , 0.3-10 g / m ² per surface area of the substrate,
Production method.
[2]
The said manufacturing method whose salt contained in the said salt aqueous solution is inorganic salt.
[3]
The said manufacturing method in which the said inorganic salt has 1 or more types selected from the group which consists of a sulfate ion, a chloride ion, an aluminum ion, an iron ion, a sodium ion, and a magnesium ion.
[4]
The above production method, wherein the inorganic salt is one or more selected from the group consisting of aluminum sulfate, ammonium sulfate, aluminum chloride, sodium sulfate, magnesium chloride and magnesium sulfate.
[5]
The said salt aqueous solution is the said manufacturing method which is salt solution whose salt concentration is 0.5-40 mass%.
[6]
The aqueous coating composition includes one or more aqueous resin dispersions selected from the group consisting of an acrylic resin emulsion, an acrylic silicone resin emulsion, a silicone resin emulsion, an epoxy resin dispersion, and an acrylic resin dispersion, Production method.
[7]
The said manufacturing method whose said coating layer is a peelable coating layer and whose said coating material is a peeling material.
[8]
A method for producing a release material having at least a substrate and a peelable coating layer, the following steps:
Providing a substrate containing 1% by mass or more of a salt with respect to the mass of the substrate;
An aqueous coating composition coating step for coating the surface of the substrate with an aqueous coating composition; and a coating layer forming step for separating moisture from the aqueous coating composition coating layer to form a peelable coating layer;
Including
The aqueous coating composition comprises one or more aqueous resin dispersions selected from acrylic silicone resin emulsions and silicone resin emulsions,
The inorganic salt is one or more selected from the group consisting of aluminum sulfate, ammonium sulfate, aluminum chloride, sodium sulfate, magnesium chloride and magnesium sulfate,
Production method.

  Even if it is a method of forming a coating layer on a substrate using an aqueous coating composition by the production method of the present invention, there is an advantage that a high production rate is possible and good manufacturability is obtained.

It is the photograph (600 times) which image | photographed the surface of the coating layer manufactured by Example 1 with the scanning electron microscope (SEM). It is the photograph (600 times) which image | photographed the surface of the paper which is a base material used in Example 1 with SEM. It is the photograph which photoed the surface with SEM, after coating only the salt solution used in Example 1 to the surface of paper which is a substrate (comparative example 3). This is a photograph (600 times) taken of the surface with SEM after directly coating the aqueous coating composition used in Example 1 on the surface of paper as a base material without coating the aqueous salt solution. Example 4). It is the photograph which photographed the surface of the coating layer obtained by painting the solvent-type coating composition of the reference example 1 with SEM (600 times).

The method of the present invention is a method for producing a coating material having at least a substrate and a coating layer, and includes the following steps:
A salt solution coating process for coating a salt solution on at least one surface of the substrate;
An aqueous coating composition coating step of further applying an aqueous coating composition to the surface of the aqueous salt solution coating, and a coating layer forming step of separating water from the aqueous coating composition coating layer to form a coating layer.
Hereinafter, the method of the present invention will be described in detail.

Substrate In the method of the present invention, any substrate such as metal, plastic, paper, wood, glass, ceramic, and mortar can be used as the substrate on which the coating layer is provided. For example, when the coating material is release paper, any paper or resin film (hereinafter referred to as “resin film”) can be used as the coating material. The “release paper” in the present specification is not limited to an embodiment in which the base material is paper, and includes an embodiment in which the base material is a resin film (so-called release film).

  It does not specifically limit as a resin film, A well-known thing can be used. Specific examples of the resin film include, for example, acrylic films such as polymethyl methacrylate; polyester films such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate films obtained from bisphenols and carbonyl chloride; nylon 6, nylon 66, nylon 12, etc. Examples thereof include nylon films; polyolefin films such as polyethylene and polypropylene; vinyl films such as polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, and polyvinylidene chloride. These resin films may be stretched or may be a composite of two or more. The resin film may also be a so-called synthetic paper made by a paper machine using a resin fiber of the synthetic resin as a raw material instead of pulp and adding a binder as necessary.

  It does not specifically limit as paper, A well-known thing can be used. Specific examples of the paper include, for example, high-quality paper, kraft paper, glassine paper, recycled paper, non-wood paper (paper obtained by taking out fibers from plants other than wood and making paper with a paper machine), and processed papers thereof. The paper may be a synthetic paper containing pulp fibers, which is made from resin fibers and pulp fibers of the above-mentioned synthetic resin, and made with a paper machine by adding a binder as required. In this specification, “synthetic paper containing pulp fibers” means that the content of pulp fibers contained in the raw material is 50% by mass or more and the content of resin fibers is less than 50% by mass.

  In the case of using paper as the base material, it is possible to use paper after the paper making process, which is a general manufacturing process of paper, and before dehydration drying. The paper in this specification means that whose pulp fiber content is 50% by mass or more.

Salt aqueous solution coating step The method of the present invention includes a salt aqueous solution coating step. In this step, an aqueous salt solution is applied to at least one surface of the substrate. By applying the aqueous salt solution, salt is present on the substrate surface.

  The salt aqueous solution is an aqueous solution containing a salt. Examples of the salt include organic salts and inorganic salts. The salt contained in the aqueous salt solution is preferably an inorganic salt. As an inorganic salt, for example, a salt having one or more selected from the group consisting of sulfate ion, chloride ion, aluminum ion, iron ion, sodium ion, magnesium ion, and when it becomes an aqueous solution, Examples include salts that liberate one or more of these ions. Examples of organic salts include carboxylates (for example, formate, acetate, citrate, oxalate, etc.) containing the above inorganic ions, organic sulfonium salts (for example, methanesulfonate, etc.), and the like. One of these salts may be included alone, or two or more thereof may be included.

  When the salt contained in the aqueous salt solution is an inorganic salt, the inorganic salt is one or more selected from the group consisting of aluminum sulfate, ammonium sulfate, aluminum chloride, sodium sulfate, magnesium chloride, and magnesium sulfate. Is more preferable, and one or more selected from the group consisting of aluminum sulfate, ammonium sulfate and aluminum chloride is more preferable. The said inorganic salt has the advantage that the performance which isolate | separates the water | moisture content contained in the coated aqueous coating composition from a composition in the subsequent coating layer formation process is excellent.

  The salt aqueous solution can be prepared by a method known to those skilled in the art using commercially available salts. The concentration of the salt contained in the salt aqueous solution is preferably in the range of 0.5 to 40% by mass, more preferably in the range of 1 to 35% by mass, and in the range of 2 to 30% by mass. It is particularly preferred.

  The salt aqueous solution may contain an organic solvent as necessary. Examples of the organic solvent that may be contained in the aqueous salt solution include alcohol solvents such as methanol, ethanol, and propanol; ketone solvents such as methyl ethyl ketone and acetone; cellosolv solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; diethylene glycol monoethyl ether; Examples include glycol solvents such as diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and ethylene glycol monobutyl ether; N-methylpyrrolidone and the like. The salt aqueous solution may contain other components as required. Examples of other components include a film-forming aid, a thickener, a surface conditioner, a preservative, a fungicide, and an antifoaming agent. When these other components are salts, it is assumed that they act together with the salt as the main component in the salt aqueous solution.

  The salt solution can be applied by a coating method generally used by those skilled in the art. Examples of the salt solution coating method include commonly used coating methods such as spraying, dipping, brushing, flow coating, roller, and roll coater.

By coating the salt solution in the salt solution coating step, salt is present on the surface of the substrate. The amount of the salt coated in the salt aqueous solution coating step is 0.3 to 10 g / m ² per surface area of the substrate. The amount of the salt to be applied is more preferably 0.5 g / m ² or more, and further preferably 1.0 g / m ² or more. Due to the presence of salt on the surface of the substrate, moisture contained in the applied aqueous coating composition is separated from the composition in the subsequent coating layer forming step.

  You may dry as needed, after coating salt aqueous solution on the base-material surface. Drying conditions can be appropriately selected according to the type of substrate. Examples of the drying conditions include conditions for drying at 30 to 120 ° C. for 2 seconds to 60 minutes. In addition, after apply | coating salt aqueous solution, an aqueous coating composition can also be applied, without drying etc.

Aqueous Coating Composition Application Step The aqueous coating composition application step is a step in which an aqueous coating composition is further applied to the surface on which the aqueous salt solution has been applied in the above step. The aqueous coating composition includes one or more aqueous resin dispersions selected from resin emulsions, cationic dispersion resins, and anionic dispersion resins.

Examples of the resin emulsion include acrylic resin emulsion, acrylic silicone resin emulsion, silicone resin emulsion, urethane resin emulsion, epoxy resin emulsion, and polyester resin emulsion. More preferably, the resin emulsion is one or more selected from an acrylic resin emulsion, an acrylic silicone resin emulsion, and a silicone resin emulsion.
Examples of the cationic dispersion resin include an epoxy resin dispersion. Examples of the anionic dispersion resin include acrylic resin dispersion.

  Examples of the acrylic resin emulsion include acrylic resin emulsions obtained by polymerization of various polymerizable monomers. The said polymerizable monomer means what has at least one unsaturated bond, such as a vinyl group, in a molecule | numerator, and the derivative | guide_body of acrylic acid and methacrylic acid is included. The polymerizable monomer is not particularly limited, and examples thereof include ethylenically unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; methyl (meth) acrylate, (meth) acrylic Ethyl unsaturated carboxylic acid alkyl ester monomers such as ethyl acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; cyclopentyl such as cyclopentyl (meth) acrylate and cyclohexyl (meth) acrylate Alkyl group-containing polymerizable monomers; monoester monomers of ethylenically unsaturated dicarboxylic acid such as ethyl maleate, butyl maleate, ethyl itaconate, butyl itaconate; 2-hydroxyethyl (meth) acrylate, ( 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) Hydroxyl group-containing ethylenically unsaturated carboxylic acid alkyl ester monomer such as a reaction product of 2-hydroxyethyl acrylate and ε-caprolactone; aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) Ethylenically unsaturated carboxylic acid aminoalkyl ester monomers such as butylaminoethyl acrylate; ethylenically unsaturated carboxylic acids such as aminoethyl (meth) acrylamide, dimethylaminomethyl (meth) acrylamide, and methylaminopropyl (meth) acrylamide Aminoalkylamide monomers; other amide group-containing ethylenically unsaturated carboxylic acid monomers such as acrylamide, methacrylamide, N-methylolacrylamide, methoxybutylacrylamide, diacetoneacrylamide; Ethylenically unsaturated carboxylic acid glycidyl ester monomers such as sidyl and glycidyl methacrylate; vinyl cyanide monomers such as (meth) acrylonitrile and α-chloroacrylonitrile; saturated aliphatic carboxylic acids such as vinyl acetate and vinyl propionate Acid vinyl ester monomers; styrene monomers such as styrene, α-methylstyrene, vinyltoluene and the like can be mentioned. These can be used alone or in combination of two or more. In the present specification, (meth) acrylic acid refers to acrylic acid or methacrylic acid.

  The acrylic resin emulsion may form an aqueous polymer dispersion in which multi-layer structured particles composed of a core part and a shell part are dispersed. The multilayer structure particle is an acrylic polymer in which the resin forming the core part has a glass transition temperature of −70 to 35 ° C., and the resin forming the shell part is an acrylic polymer having a glass transition temperature of 25 to 80 ° C. It is preferable. An aqueous polymer dispersion in which such multilayer structure particles are dispersed can be prepared by a known production method described in JP-A No. 2002-12816.

  The glass transition temperature of the acrylic polymer can be calculated based on the known glass transition temperature and composition ratio of the constituent monomer or homopolymer.

  The acrylic resin emulsion preferably has a particle size of 20 to 500 nm, and more preferably 50 to 200 nm. When the particle diameter is less than 20 nm, the viscosity of the aqueous coating composition increases, and more diluent is required to ensure coating workability, and the solid content concentration of the aqueous coating composition may be significantly reduced. If the thickness exceeds 500 nm, the stability of the acrylic resin emulsion may be significantly reduced. In the present specification, the particle diameter is a weight average particle diameter determined by a dynamic light scattering method, and specifically, an electrophoretic light scattering photometer ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) and the like. Can be measured using.

  Examples of the acrylic silicone resin emulsion include a polymer obtained by polymerization of a monomer composition further containing an alkoxysilyl group-containing polymerizable monomer in addition to the polymerizable monomer.

  The alkoxysilyl group-containing polymerizable monomer is not particularly limited as long as it is a polymerizable monomer containing an alkoxysilyl group having 1 to 14 carbon atoms. For example, trimethoxysilylpropyl (meth) acrylate, ( (Meth) acrylic acid triethoxysilylpropyl, (meth) acrylic acid tributoxysilylpropyl, (meth) acrylic acid dimethoxymethylsilylpropyl, (meth) acrylic acid methoxydimethylsilylpropyl, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Examples include dimethoxymethylsilane, vinylmethoxydimethylsilane, and vinyltris (β-methoxyethoxy) silane. These can be used alone or in combination of two or more. Among these, in particular, trimethoxysilylpropyl (meth) acrylate, triethoxysilylpropyl (meth) acrylate, vinyltrimethoxysilane, vinyltriethoxysilane and the like can be mentioned.

  Furthermore, the acrylic silicone resin emulsion may introduce an organic silicone unit into the acrylic resin. As a method for introducing an organosilicone unit, a mixture of an organosilicone compound and an acrylic polymerizable monomer is emulsion-polymerized and subjected to hydrolysis, condensation reaction and radical polymerization, and a monomer having a silicone functional group is copolymerized. Examples thereof include a method, a method of bonding an organosilicone compound to the surface of acrylic polymer particles by reacting an organosilicone compound with an acrylic polymer. Two or more methods described above may be combined.

The organosilicon compound used in the above method is not particularly limited, and examples thereof include organosilane, hydrolyzate of organosilane, and condensate of organosilane.

  The organosilane is generally represented by the following general formula (1)

［式中、Ｒ^１は、２個存在するときは同一または異なり、炭素数１〜８の一価の有機基を示す。Ｒ^２は、同一または異なり、炭素数１〜５のアルキル基または炭素数１〜６のアシル基を示す。ｎは０〜２の整数である。］
で表される。

[Wherein, R ¹ is the same or different when two are present, and represents a monovalent organic group having 1 to 8 carbon atoms. R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms. n is an integer of 0-2. ]
It is represented by

The organosilane hydrolyzate is a compound in which the OR ² group of the organosilane represented by the general formula (1) is hydrolyzed. It is not necessary that all ² to 4 OR ² groups contained in the organosilane are hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or A mixture thereof may be used.

  The organosilane condensate is obtained by condensing silanol groups of an organosilane hydrolyzate to form a Si-O-Si bond. The organosilicone compound may be a mixture of all of the silanol groups, a mixture of a small part of the silanol groups, or a mixture of those having different degrees of condensation.

In the general formula (1), examples of the monovalent organic group having 1 to 8 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. Group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and other alkyl groups; acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group Acyl groups such as trioyl group and caproyl group; vinyl group, allyl group, cyclohexyl group, phenyl group, epoxy group, glycidyl group, (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate group, etc. In addition to these, substituted derivatives of these groups can be mentioned.

Examples of the substituent in the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a (meth) acryloxy group. Ureido groups, ammonium bases and the like. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent. In the general formula (1), when two R ¹ are present, they may be the same as or different from each other.

The alkyl group having 1 to 5 carbon atoms for ^{R 2,} for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, sec- butyl group, t- butyl radical, n -A pentyl group etc. can be mentioned, As a C1-C6 acyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a caproyl group etc. can be mentioned, for example. A plurality of R ² present in the general formula (1) may be the same as or different from each other.

  The organosilane is not particularly limited, and examples thereof include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane; Methoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltri Methoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltol Ethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxy Silane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxy Propyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropi Trimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) attaacryloxy Trialkoxysilanes such as propyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, di Ethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n -Butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di- n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. In addition to dialkoxysilanes, Triacetyl silane, and dimethyl di acetyloxy silane.

  Of these, trialkoxysilanes and dialkoxysilanes are preferably used. As the trialkoxysilanes, methyltrimethoxysilane and methyltriethoxysilane are preferable, and dialkoxysilanes are more preferable. Is preferably dimethyldimethoxysilane or dimethyldiethoxysilane.

  Silicone resin emulsions can be prepared by emulsifying organopolysiloxane in water in the presence of a surfactant. In the preparation of the silicone resin emulsion, additives such as a crosslinking agent and a catalyst may be included as necessary.

  As the organopolysiloxane, an organopolysiloxane such as a non-reactive organopolysiloxane, a condensed organopolysiloxane, or an addition organopolysiloxane can be used. One of these organopolysiloxanes may be used alone, or two or more thereof may be used in combination.

  Examples of the non-reactive organopolysiloxane include a polymer having a siloxane bond constituted by a siloxane group having a saturated hydrocarbon group.

（２）
上記式（２）中、Ｒ^３〜Ｒ^１０はそれぞれ独立して、置換基を有してもよい、炭素数１〜２０の一価の飽和炭化水素基であり、ｎは２５〜２０００の整数である。
上記式（２）中、Ｒ^３〜Ｒ^１０は、それぞれ独立して、メチル基、エチル基、プロピル基、ブチル基などのアルキル基、シクロヘキシル基などのシクロアルキル基、フェニル基、トリル基などのアリール基、あるいはこれらの基の炭素原子に結合した水素原子の一部または全部をハロゲン原子、シアノ基などで置換したクロロメチル基、シアノエチル基などのような非置換または置換された一価の飽和炭化水素基などから選択される基であるのが好ましい。上記式（２）で示される非反応型オルガノポリシロキサンにおいて、Ｒ^３〜Ｒ^１０のうち少なくとも８０％がメチル基であるのがより好ましい。 The non-reactive organopolysiloxane can be represented by, for example, the following formula (2).

(2)
In the formula ^{(2), R} 3 ~R ¹⁰ are each independently, may have a substituent, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, n represents an integer of 25 to 2000 It is.
In the above formula (2), R ^{3 to} R ¹⁰ are each independently an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group or a tolyl group. Unsubstituted or substituted monovalent saturation such as chloromethyl group, cyanoethyl group, etc., wherein aryl group or part or all of hydrogen atoms bonded to carbon atom of these groups are substituted with halogen atom, cyano group, etc. A group selected from hydrocarbon groups and the like is preferable. In the non-reactive organopolysiloxane represented by the above formula (2), it is more preferable that at least 80% of R ^{3 to} R ¹⁰ is a methyl group.

The condensed organopolysiloxane is an organopolysiloxane in which at least two monovalent saturated hydrocarbon groups are substituted with hydroxyl groups among the non-reactive organopolysiloxanes. As the condensed organopolysiloxane, for example, an organopolysiloxane represented by the above formula (2), wherein R ³ and R ⁷ are hydroxyl groups, and R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and n is an integer of 25 to 2000, and examples thereof include organopolysiloxane. In this embodiment, it is more preferred that at least 80% of R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ is a methyl group.

The addition type organopolysiloxane is an organopolysiloxane in which at least two monovalent saturated hydrocarbon groups are substituted with alkenyl groups among the non-reactive type organopolysiloxanes.
As an addition type organopolysiloxane, for example, an organopolysiloxane represented by the above formula (2), wherein at least two of R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ are alkenyl groups. And the remaining groups are each independently a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁵ and R ⁹ are each independently substituted Examples thereof include organopolysiloxane, which represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a group, and n is an integer of 25 to 2,000.

  Examples of the alkenyl group include monovalent hydrocarbon groups having 1 to 10 carbon atoms and having a carbon-carbon unsaturated double bond group at the terminal thereof. Specific examples of the alkenyl group include a vinyl group and a prop-2-en-1-yl group. The alkenyl group is more preferably a vinyl group.

In such an addition-type organopolysiloxane, it is more preferable that at least 80% of monovalent saturated hydrocarbon groups which R ^{3 to} R ¹⁰ can take are methyl groups.

  Another example of the addition type organopolysiloxane is an organopolysiloxane represented by the following formula (3).

（３）
上記式（３）中、Ｒ^３、Ｒ^４、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^１０のうち少なくとも１つはアルケニル基であり、そして残りの基は、それぞれ独立して、置換基を有してもよい、炭素数１〜２０の一価の飽和炭化水素基であり、
Ｒ^５、Ｒ^９およびＲ^１２はそれぞれ独立して、置換基を有してもよい、炭素数１〜２０の一価の飽和炭化水素基を示し、
Ｒ^１１は、アルケニル基であり、
ｐおよびｑはそれぞれ独立した整数であって、２５＜ｐ＋ｑ＜２０００を満たすことを条件とする。

(3)
In the above formula (3), at least one of R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ is an alkenyl group, and the remaining groups each independently have a substituent. A monovalent saturated hydrocarbon group having 1 to 20 carbon atoms,
R ⁵ , R ⁹ and R ¹² each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent,
R ¹¹ is an alkenyl group,
p and q are independent integers, and satisfy 25 < p + q < 2000.

  Preferred alkenyl groups in the addition type organopolysiloxane are the same as described above.

In the addition type organopolysiloxane, it is more preferable that at least 80% of the monovalent saturated hydrocarbon groups which R ^{3 to} R ¹² can take are methyl groups.

  Examples of the surfactant that can be used in the preparation of the silicone resin emulsion using the organopolysiloxane include an anionic surfactant, a cationic surfactant, and a nonionic surfactant. As the surfactant, an anionic surfactant or a cationic surfactant is preferably used. Examples of the anionic surfactant include those having a sulfonic acid group, a sulfonate group, a sulfate ester group, a phosphate ester group, a carboxyl group, and the like. Examples of the cationic surfactant include those having structures of amine salt, quaternary ammonium salt and polyoxyalkylene addition type ammonium salt. Examples of nonionic surfactants include alkyl ether types such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether, and alkyl ester types such as polyoxyethylene oleate and polyoxyethylene laurate. . One of these anionic surfactants or cationic surfactants may be used alone, or two or more thereof may be used in combination. A nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant. It is more preferable to use an anionic surfactant or a cationic surfactant in combination with a nonionic surfactant having an HLB of 10 to 15 in terms of the stability of the resulting silicone resin emulsion.

  The surfactant used for preparing the emulsion is preferably in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the organopolysiloxane.

  In preparing a silicone resin emulsion using an organopolysiloxane, a water-soluble resin such as polyvinyl alcohol (PVA) may be used as necessary. In the preparation of a silicone resin emulsion, such a water-soluble resin has the same effect as a surfactant and has the advantage that the stability of the resulting silicone resin emulsion can be improved. In the case where a water-soluble resin is used in the preparation of the emulsion, the amount of the water-soluble resin used is preferably in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the organopolysiloxane.

  In the preparation of the silicone resin emulsion, a crosslinking agent may be used as necessary. For example, when a condensed organopolysiloxane and / or an addition-type organopolysiloxane is used as the organopolysiloxane, it is an organohydrogenpolysiloxane or an organopolysiloxane having at least three SiH or hydrolyzable groups in one molecule. A thing can be used suitably as a crosslinking agent. Examples of the hydrolyzable group include an alkoxy group (for example, methoxy group, ethoxy group, etc.) directly bonded to Si element.

  Preferred examples of the crosslinking agent include methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, polymethoxy polysiloxane, polyethoxy polysiloxane and the like.

（４）
上記式（４）中、ｅは、５〜３００の範囲内の整数である。 Preferable methyl hydrogen polysiloxane includes, for example, polysiloxane represented by the following formula (4).

(4)
In said formula (4), e is an integer in the range of 5-300.

（５）
上記式（５）中、ｆは、５〜３００の範囲内の整数である。 Preferable polyethoxypolysiloxane includes, for example, polysiloxane represented by the following formula (5).

(5)
In said formula (5), f is an integer in the range of 5-300.

（６）
上記式（６）中、ｇは、５〜３００の範囲内の整数である。 Preferable polymethoxypolysiloxane includes, for example, polysiloxane represented by the following formula (6).

(6)
In said formula (6), g is an integer in the range of 5-300.

  By crosslinking the organopolysiloxane using a cross-linking agent, for example, when providing a release layer, there are advantages such as improving water repellency and non-adhesiveness and increasing the sustainability of these effects. is there.

  When using a crosslinking agent, it is preferable to use within the range of 0.1-20 mass parts with respect to 100 mass parts of organopolysiloxane.

  In preparing the silicone resin emulsion, a catalyst may be used as necessary. For example, when a condensation-type organopolysiloxane is used as the organopolysiloxane, there is an advantage that the crosslinking reaction can be favorably progressed by using a condensation reaction catalyst. Examples of condensation reaction catalysts include acid catalysts such as hydrochloric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, maleic acid, and trifluoroacetic acid; alkalis such as sodium hydroxide, potassium hydroxide, sodium ethoxide, and tetraethylammonium hydroxide. Catalyst; and sodium carbonate, alkoxide, chelate compound and the like.

  For example, when an addition-type organopolysiloxane is used as the organopolysiloxane, there is an advantage that the crosslinking reaction can be favorably progressed by using an addition reaction catalyst. Examples of the addition reaction catalyst include platinum black, chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alcohol coordination compound, rhodium, rhodium-olefin complex, and the like.

  When using a catalyst, it is preferable to use within the range of 0.001-3 mass parts with respect to 100 mass parts of organopolysiloxane. The amount of catalyst in the case of using a catalyst can be appropriately selected according to the type of catalyst and the required reaction rate.

  The silicone resin emulsion can be prepared by emulsifying (dispersing) the above components using a known method. For example, an organopolysiloxane, water, a surfactant, and an optional cross-linking agent are mixed using a stirrer (for example, a high-shearing stirrer such as a planetary mixer or a combination mixer), and the phase inversion method is performed. It can be prepared by emulsifying and diluting with water. When a catalyst is used in the preparation of the silicone resin emulsion, it is preferably added after being dispersed or emulsified separately from the emulsification step.

  In preparation of silicone resin emulsion, water-soluble resin (for example, PVA, cellulose derivative, starch derivative, etc.), catalyst activity inhibitor, silicone resin, silica, leveling agent, styrene / maleic anhydride copolymer, etc. Can be added. The addition amount of such an arbitrary component can be made into the amount normally used by those skilled in the art, provided that the effects of the present invention are not hindered.

  Urethane resin emulsions, epoxy resin emulsions, polyester resin emulsions, and cationic dispersion resins such as epoxy resin dispersions and anionic dispersion resins such as acrylic resin dispersions can be prepared according to methods commonly used by those skilled in the art. .

  For example, the acrylic resin dispersion can be prepared by solution polymerization of the polymerizable monomer to prepare an acrylic resin, and then dispersing the obtained acrylic resin in water. More specifically, the acrylic resin dispersion has the above-mentioned ethylenically unsaturated carboxylic acid monomer as an essential component, and after performing solution polymerization with other polymerizable monomers, it is neutralized with a basic compound. It can be prepared by dispersing in water.

  The solution polymerization is generally a method in which the mixture of the polymerizable monomers is stirred while being dropped into an organic solvent together with a polymerization initiator under heating conditions. Solution polymerization can be performed, for example, under conditions of a polymerization temperature of 60 to 160 ° C. and a dropping time of 0.5 to 10 hours. The polymerizable monomer can be polymerized in two stages. By polymerizing the polymerizable monomer in two stages, a core-shell type acrylic resin dispersion comprising a core part and a shell part can be obtained.

  The said polymerization initiator will not be specifically limited if it is used for normal polymerization, For example, an azo compound or a peroxide is mentioned. Generally, the amount of the polymerization initiator with respect to 100 parts by mass of the polymerizable monomer mixture is 0.1 to 18 parts by mass, preferably 0.3 to 12 parts by mass.

  Moreover, the solvent which can be used here will not be specifically limited if it does not have a bad influence on reaction, For example, alcohol, a ketone, ether, a hydrocarbon solvent, etc. are mentioned. Further, in order to adjust the molecular weight, a mercaptan such as lauryl mercaptan and a chain transfer agent such as α-methylstyrene dimer can be used as necessary.

  Thus, the number average molecular weight of the acrylic resin obtained by solution polymerization is preferably 4,000 to 20,000. In this specification, the number average molecular weight of the acrylic resin obtained by solution polymerization can be measured by gel permeation chromatography (GPC) using a polystyrene standard sample standard.

  The acrylic resin obtained by the solution polymerization can be obtained by removing the solvent as necessary, and then adding a basic compound to neutralize and make it aqueous, thereby obtaining an acrylic resin dispersion. The amount of the basic compound added is preferably such that the neutralization rate of the carboxyl group of the acrylic resin obtained by the solution polymerization is 60 to 100%. The basic compounds are ammonia, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, dimethylethanolamine, diethanolamine, diethylaminoethanol, triethanolamine, tetraethylammonium hydroxide, propylamine, dipropylamine, tripropylamine. , Amines such as butylamine, dibutylamine, and tributylamine.

  The amount of the aqueous resin dispersion containing one or more selected from a resin emulsion, a cationic dispersion resin, and an anionic dispersion resin contained in the aqueous coating composition is an aqueous coating composition 100 as a resin solid content. It is preferable that it is 1-50 mass parts with respect to a mass part.

  The aqueous coating composition may contain other components as required in addition to the above components. As other components, for example, a film-forming aid, a thickener, a polyfunctional amine polymer, a coupling agent, a plasticizer, a crosslinked resin particle, a pigment, a surface conditioner, an antiseptic, an antifungal agent, an antifoaming agent, Examples thereof include a light stabilizer, an ultraviolet absorber, an antioxidant, and a pH adjuster.

  The aqueous coating composition contains water as a solvent. The aqueous coating composition may optionally contain a hydrophilic organic solvent such as alcohol or glycol, in addition to water.

  It does not specifically limit as a preparation method of an aqueous coating composition, It can prepare by stirring each component mentioned above with a stirrer etc. When pigments or design materials are included in the aqueous coating composition, those having good dispersibility can be mixed with a stirrer, and other methods include sand grinding in a vehicle containing water, a surfactant or a dispersant, etc. What was previously disperse | distributed using the mill etc. can also be added.

  The aqueous coating composition is further coated on the surface coated with the salt aqueous solution in the salt aqueous solution coating step. The aqueous coating composition can be applied by a coating method commonly used by those skilled in the art. Examples of the coating method include rollers, roll coaters, air sprays, airless sprays, air knife coaters, curtain flow coaters, roller curtain coaters, die coaters, gravure coaters, wire coaters, doctor coaters, blade coaters, and the like.

The coating amount of the aqueous coating composition can be appropriately selected according to the type, performance and solid content of the aqueous coating composition, and the type and performance of the coating layer to be provided. For example, the coating layer can be applied in an amount of 0.1 to 200 g / m ² as the dry mass. As dry mass of a coating layer, 0.2-150 g / m < ² > is preferable and 0.3-100 g / m < ² > is more preferable.

Coating layer formation process In the method of this invention, a water | moisture content is isolate | separated from the aqueous coating composition coating layer coated in the said coating layer formation process, and a coating layer is formed. In the method of the present invention, the aqueous coating composition and the salt present on the substrate surface come into contact with each other when the aqueous coating composition is applied to the surface of the base material coated with the aqueous salt solution. And by this contact, the dispersion state of aqueous resin dispersions, such as a resin emulsion contained in an aqueous coating composition, will become unstable, and a resin component will aggregate. It is considered that the charge of the aqueous resin dispersion such as a resin emulsion is neutralized by the opposite charge of the salt and the salting-out action lowers the stability of the aqueous resin dispersion. Thereby, the water | moisture content contained in an aqueous coating composition will isolate | separate, and a coating layer will be formed in a short time.

  In the coating layer forming step of the present invention, the aqueous resin dispersion in the composition is brought into a predetermined unstable condition by contacting the salt present on the substrate surface with the aqueous coating composition as described above. Thus, the resin component and the like are intentionally agglomerated to precipitate, thereby separating the resin component constituting the aqueous resin dispersion and moisture. In the coating layer forming step, the time required for forming the coating layer is shortened by separating the moisture and forming the coating layer as described above. Thereby, there is an advantage that the time required for forming the coating layer is shortened and the production speed of the coating material is increased.

  The “water content” separated in the coating layer forming step is not limited to water. The “water” to be separated may include, for example, a water-soluble component (such as a surfactant) that can be contained in the aqueous coating composition, an organic solvent (such as alcohol), and the like.

  In the method of the present invention, in the coating layer forming step, moisture separated from the applied aqueous coating composition may be removed by a method other than drying. By removing the water separated from the composition by a method other than drying, the time required for forming the coating layer can be further shortened. As a method of removing moisture by a method other than drying, for example, a method of draining moisture by gravity by tilting a coating layer obtained by painting, removing moisture by hand or air (air blow), or as necessary And a removal method such as removal using an arbitrary instrument, and a method of removing moisture by contacting a moisture-absorbing material (for example, a superabsorbent resin, protein, polysaccharide, etc.) to absorb moisture.

  In the method of the present invention, it is sufficient that water is separated from the coating layer of the aqueous coating composition by contact between the salt and the aqueous coating composition. For example, the obtained coating layer may be heated and dried and cured as necessary. Examples of the heating condition include a condition of heating at 30 to 150 ° C. for 15 seconds to 60 minutes. The “curing” is particularly preferably used in an embodiment in which an aqueous coating composition containing a silicone resin emulsion containing an addition-type organopolysiloxane and / or a condensation-type organopolysiloxane is applied.

As an embodiment of the method of the present invention, an embodiment in which the coating layer is a peelable coating layer and the coating material is a release material. In such an embodiment, the aqueous coating composition used for forming the peelable coating layer preferably contains one or more aqueous resin dispersions selected from acrylic silicone resin emulsions and silicone resin emulsions.
Examples of a method for producing a release material having at least a substrate and a release coating layer include a method including the following steps:
Providing a substrate containing 1% by mass or more of a salt with respect to the mass of the substrate;
An aqueous coating composition coating step of coating an aqueous coating composition on the surface of the substrate; and a coating layer forming step of separating moisture from the aqueous coating composition coating layer to form a peelable coating layer.
The aqueous coating composition preferably comprises one or more aqueous resin dispersions selected from acrylic silicone resin emulsions and silicone resin emulsions,
The inorganic salt is preferably one or more selected from the group consisting of aluminum sulfate, ammonium sulfate, aluminum chloride, sodium sulfate, magnesium chloride and magnesium sulfate, and from the group consisting of aluminum sulfate, ammonium sulfate and aluminum chloride. More preferably, it is one or more selected.

  Among the above steps, “the step of providing a base material containing a salt of 1% by mass or more with respect to the mass of the base material” may be provided by coating the above-mentioned aqueous salt solution on the surface of the base material. You may provide by manufacturing so that 1 mass% or more of salt may be included at the time of manufacture of a base material. The amount of salt contained in the substrate is preferably 3% by mass or more with respect to the mass of the substrate.

  As another embodiment of the method of the present invention, there is an embodiment in which the coating material is so-called coated paper. In such an embodiment, the aqueous coating composition used to form the coating layer comprises one or more aqueous resin dispersions selected from acrylic resin dispersions, acrylic resin emulsions and acrylic silicone resin emulsions. preferable.

  The method of the present invention has an advantage that, for example, in the production of release paper, it is not necessary to form a sealing layer (barrier layer) before forming the release layer. Paper or a film is generally used as a base material for the release paper. Here, when paper is used as the substrate, it is necessary to provide a sealing layer (barrier layer) on the surface of the substrate (paper) in advance before providing the release layer. Paper has many voids between pulp fibers. Therefore, if the release layer forming composition is applied as it is onto the substrate surface, the release layer composition penetrates into the interior of the paper, making it difficult to suitably provide the release layer. For example, Japanese Unexamined Patent Publication No. 2017-038772 discloses a paper coating agent containing polyvinyl alcohol that can be suitably used for forming a sealing layer (barrier layer) in the production of release paper. As another method, a method of forming a sealing layer (barrier layer) by extruding molten polyethylene into a film and laminating it on paper is generally used.

  For example, when producing release paper by the method of the present invention, it has been experimentally found that a release layer can be suitably formed without forming a sealing layer (barrier layer) as described above. This is because salt exists on the surface of a substrate such as paper, and the composition penetrates into the interior of the substrate by contact with the salt and the coating composition to quickly separate moisture and form a coating layer. This is thought to be hindered. The method of the present invention has an advantage that the step of forming the sealing layer (barrier layer) as described above can be omitted.

  The following examples further illustrate the present invention, but the present invention is not limited thereto. In the examples, “parts” and “%” are based on mass unless otherwise specified.

Preparation Example 1 Preparation of Silicone Resin Emulsion A 100 parts by mass of polyorganosiloxane represented by the following formula as addition-type organopolysiloxane was added to the composite emulsification apparatus (5 L).

架橋剤として、メチルハイドロジエンポリシロキサン（（ＣＨ_３）_３ＳｉＯ−（ＳｉＨＣＨ_３Ｏ）_４０−Ｓｉ（ＣＨ_３）_３）を６質量部、界面活性剤としてドデシルベンゼンスルホン酸ナトリウム１質量部とポリオキシエチレンラウリルエーテル（ＨＬＢ：１３．６）１質量部、ＰＶＡ（ポリビニルアルコール）樹脂（ケン化度９０モル％）５質量部（予め１０％水溶液に調整したもの５０質量部として使用）、触媒活性抑制剤としてエチニルシクロヘキサノール０．４質量部を入れて、均一に撹拌混合した。

As a crosslinking agent, 6 parts by mass of methylhydropolyenepolysiloxane ((CH ₃ ) ₃ SiO— (SiHCH ₃ O) ₄₀ —Si (CH ₃ ) ₃ ), 1 part by mass of sodium dodecylbenzenesulfonate as a surfactant and poly 1 part by mass of oxyethylene lauryl ether (HLB: 13.6), 5 parts by mass of PVA (polyvinyl alcohol) resin (degree of saponification 90 mol%) (previously adjusted to 10% aqueous solution and used as 50 parts by mass), catalytic activity 0.4 part by mass of ethynylcyclohexanol was added as an inhibitor, and the mixture was stirred and mixed uniformly.

  To this mixture, 10 parts by mass of water was added to cause phase inversion, followed by stirring for 30 minutes. 166 parts by mass of additional water was added, diluted and stirred to obtain a silicone resin emulsion A (solid content of organopolysiloxane: 30% by mass).

Preparation Example 2 Preparation of aqueous coating composition (1) 1 part by weight of PVA resin (saponification degree 90 mol%) and 130 parts by weight of water were mixed and stirred until a uniform solution was obtained, and the silicone resin emulsion of Preparation Example 1 20 parts by mass of A and platinum catalyst CAT-PM-10A (manufactured by Shin-Etsu Chemical Co., Ltd.) are added and mixed with 0.9 part by mass (platinum mass with respect to organopolysiloxane: 150 ppm), and an aqueous coating composition (1) is prepared. Obtained. This aqueous coating composition (1) contains the silicone resin emulsion A as an aqueous resin dispersion.

Preparation Example 3 Preparation of Acrylic Silicone Resin Emulsion 50 parts by mass of deionized water and 0.5 part by mass of Aqualon HS10 (Daiichi Kogyo Seiyaku Co., Ltd.) as a reactive emulsifier were placed in a reaction vessel, and the temperature of the contents was 85 ° C. . Among them, 20 parts by mass of methyl methacrylate, 5 parts by mass of styrene, 5 parts by mass of butyl acrylate, 0.5 parts by mass of acrylic acid, 20 parts by mass of deionized water, and 0.3 parts by mass of Aqualon HS10 (Daiichi Kogyo Seiyaku Co., Ltd.) A pre-emulsified solution and a polymerization initiator aqueous solution consisting of 0.1 parts by weight of ammonium persulfate as a water-soluble polymerization initiator and 10 parts by weight of deionized water were dropped in 2 hours to prepare a shell part. During the emulsion polymerization, the pH of the polymerization reaction solution was kept at 3.0. Then, 20 parts by mass of cyclohexyl methacrylate, 20 parts by mass of butyl acrylate, 20 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of methyl methacrylate, 1.0 part by mass of acrylic acid, 3 parts by mass of trimethoxysilylpropyl methacrylate, 40 deionized water A pre-emulsion solution consisting of 1.0 part by mass of AQUALON HS10 (Daiichi Kogyo Seiyaku Co., Ltd.) and an aqueous solution of polymerization initiator consisting of 0.2 part by mass of ammonium persulfate and 10 parts by mass of deionized water are added dropwise over 2 hours. Then, stirring was further continued for 3 hours to prepare a core part. The reaction temperature was cooled to 30 ° C., 5.5 parts by mass of 10% ammonia water was added to adjust the pH to 8.5, and an acrylic silicone resin emulsion having a nonvolatile content concentration of 45% was obtained.

Preparation Example 4 Preparation of Aqueous Coating Composition (2) 1 part by weight of PVA resin (saponification degree 90 mol%) and 136 parts by weight of water are mixed and stirred until a uniform solution is obtained. 15 parts by mass of the emulsion was mixed to obtain an aqueous coating composition (2). This aqueous coating composition (2) contains an acrylic silicone resin emulsion as an aqueous resin dispersion.

Preparation Example 5 Preparation of Silicone Resin Emulsion B 100 parts by mass of polyorganosiloxane represented by the following formula as addition type organopolysiloxane was added to the composite emulsification apparatus (5L).

架橋剤として、メチルハイドロジエンポリシロキサン（（ＣＨ_３）_３ＳｉＯ−（ＳｉＨＣＨ_３Ｏ）_４０−Ｓｉ（ＣＨ_３）_３）を６質量部、界面活性剤としてセチルトリメチルアンモニウムクロリド１質量部とポリオキシエチレンラウリルエーテル（ＨＬＢ：１３．６）１質量部、ＰＶＡ樹脂（ケン化度９０モル％）５質量部（予め１０％水溶液に調整したもの５０質量部として使用）、触媒活性抑制剤としてエチニルシクロヘキサノール０．４質量部を入れて、均一に撹拌混合した。

As a crosslinking agent, 6 parts by mass of methylhydropolyene polysiloxane ((CH ₃ ) ₃ SiO— (SiHCH ₃ O) ₄₀ —Si (CH ₃ ) ₃ ), 1 part by mass of cetyltrimethylammonium chloride and polyoxy as a surfactant 1 part by mass of ethylene lauryl ether (HLB: 13.6), 5 parts by mass of PVA resin (degree of saponification 90 mol%) (previously adjusted to 10% aqueous solution and used as 50 parts by mass), ethinylcyclo as a catalyst activity inhibitor 0.4 parts by mass of hexanol was added and stirred and mixed uniformly.

  To this mixture, 10 parts by mass of water was added to cause phase inversion, followed by stirring for 30 minutes. 166 parts by mass of additional water was added, diluted and stirred to obtain a silicone resin emulsion B (solid content of organopolysiloxane: 30% by mass).

Preparation Example 6 Preparation of aqueous coating composition (3) 1 part by weight of PVA resin (saponification degree 90 mol%) and 130 parts by weight of water were mixed and stirred until a uniform solution was obtained, and the silicone resin emulsion of Preparation Example 5 20 parts by mass of B and 0.9 parts by mass of platinum catalyst CAT-PM-10A (manufactured by Shin-Etsu Chemical Co., Ltd.) (platinum mass with respect to organopolysiloxane: 150 ppm) were added and mixed to prepare an aqueous coating composition (3). Obtained. This aqueous coating composition (3) contains silicone resin emulsion B as an aqueous resin dispersion.

Example 1
Preparation of salt aqueous solution A salt solution containing 1% by mass of salt by mixing ion-exchanged water to 100 parts by mass in a beaker containing 1 part by mass of aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) as a salt. 100 parts by mass were obtained.

Glassine paper (weighing 60 g / m ² ) was used as a production base for the coating material .
The salt aqueous solution obtained above was applied to the surface of glassine paper (base material) using a # 22 bar coater so that the surface area of the base material was 0.5 g / m ² . Subsequently, it dried for 60 second in a 100 degreeC hot-air circulation type drying furnace.
Apply the aqueous coating composition (1) obtained in Preparation Example 2 on the surface coated with the above-described salt aqueous solution using a # 12 bar coater so that the solid content per surface of the substrate is 1 g / m ^2. did. Ten seconds after coating, moisture was blown off by air blow (discharge pressure 4 kg / m ² ).
Subsequently, the coating material (peeling material) which has a coating layer was obtained by heating and drying for 60 seconds in a 120 degreeC hot-air circulation type drying furnace, and advancing drying and addition reaction.

Example 2
A salt solution containing 1.66% by mass of salt by adding ion-exchanged water to 100 parts by mass in a beaker containing 1.66 parts by mass of aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) as a salt. 100 parts by mass were obtained.
A coating material (peeling material) was obtained in the same manner as in Example 1 except that the salt aqueous solution obtained above was applied so that the amount of salt shown in the following table was applied.

Example 3
A salt solution containing 3.34% by mass of salt by adding ion-exchanged water to 100 parts by mass in a beaker containing 3.34 parts by mass of aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) as a salt. 100 parts by mass were obtained.
A coating material (peeling material) was obtained in the same manner as in Example 1 except that the salt aqueous solution obtained above was applied so that the amount of salt shown in the following table was applied.

Example 4
In a beaker containing 1.66 parts by mass of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) as a salt, ion exchange water is added to make 100 parts by mass, and then mixed to obtain an aqueous salt solution 100 containing 1.66% by mass of salt. A mass part was obtained.
A coating material (peeling material) was obtained in the same manner as in Example 1 except that the salt aqueous solution obtained above was applied so that the amount of salt shown in the following table was applied.

Example 5
In a beaker containing 3.34 parts by mass of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) as a salt, ion exchange water is added to 100 parts by mass, and then mixed to obtain an aqueous salt solution 100 containing 3.34% by mass of salt. A mass part was obtained.
A coating material (peeling material) was obtained in the same manner as in Example 1 except that the salt aqueous solution obtained above was applied so that the amount of salt shown in the following table was applied.

Example 6
In a beaker containing 1.66 parts by mass of aluminum chloride (AlCl ₃ ) as a salt, ion exchange water is added to 100 parts by mass, and then mixed to obtain 100 parts by mass of an aqueous salt solution containing 1.66% by mass of the salt. It was.
A coating material (peeling material) was obtained in the same manner as in Example 1 except that the salt aqueous solution obtained above was applied so that the amount of salt shown in the following table was applied.

Example 7
In a beaker containing 3.34 parts by mass of sodium chloride (NaCl) as a salt, ion exchange water was added to make 100 parts by mass, and then mixed to obtain 100 parts by mass of an aqueous salt solution containing 3.34% by mass of salt. .
A coating material (peeling material) was obtained in the same manner as in Example 1 except that the salt aqueous solution obtained above was applied so that the amount of salt shown in the following table was applied.

Example 8
An aqueous salt solution was prepared in the same manner as in Example 1, and the obtained aqueous salt solution was coated in the same manner as in Example 1.
Instead of the aqueous coating composition (1), the aqueous coating composition (2) obtained in Preparation Example 4 has a solid content of 1 g / m ² per surface of the base material on the surface coated with the salt aqueous solution. As above, it was painted using a # 12 bar coater. Ten seconds after coating, moisture was blown off by air blow (discharge pressure 4 kg / m ² ), and then heat-dried in a 120 ° C. hot air circulation drying oven for 60 seconds to obtain a coating material (coated paper). .

Example 9
An aqueous salt solution was prepared in the same manner as in Example 1, and the obtained aqueous salt solution was coated in the same manner as in Example 1.
Instead of the aqueous coating composition (1), the aqueous coating composition (3) obtained in Preparation Example 6 has a solid content of 1 g / m ² per surface of the base material on the surface coated with the aqueous salt solution. As above, it was painted using a # 12 bar coater. Ten seconds after coating, moisture was blown off by air blow (discharge pressure 4 kg / m ² ), and then heat-dried in a 120 ° C. hot-air circulating drying furnace for 60 seconds to obtain a coating material (peeling material). .

Comparative Example 1
A salt aqueous solution containing 0.32% by mass of salt by adding ion-exchanged water to 100 parts by mass in a beaker containing 0.32 parts by mass of aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) as a salt. 100 parts by mass were obtained.
A coating material (peeling material) was obtained in the same manner as in Example 1 except that the salt aqueous solution obtained above was applied so that the amount of salt shown in the following table was applied.

Comparative Example 2
Comparative Example 2 is a comparative example using a resin aqueous solution instead of the salt aqueous solution.
A beaker containing 5 parts by mass of polyvinyl alcohol (Kuraray Kuraray Poval PVA105) instead of salt is charged with 100 parts by mass of ion-exchanged water, and then mixed to obtain 100% by mass of an aqueous resin solution containing 5% by mass of polyvinyl alcohol. Got a part.
The obtained aqueous resin solution was coated on the surface of glassine paper (base material) using a # 8 bar coater so that the amount of resin per surface area of the base material was 0.83 g / m ² . Subsequently, it dried for 60 second in a 100 degreeC hot-air circulation type drying furnace.
The aqueous coating composition (1) obtained in Preparation Example 2 was applied to the surface coated with the resin aqueous solution using a # 12 bar coater so that the solid content per surface of the substrate was 1 g / m ^2. did. Ten seconds after coating, moisture was blown off by air blow (discharge pressure 4 kg / m ² ).
Subsequently, it heated for 60 second in the 120 degreeC hot-air circulation type drying furnace, the drying and the addition reaction were advanced, and the coating material (peeling material) was obtained.

Comparative Example 3
After applying the aqueous salt solution in the same manner as in Example 1, a coating material was obtained without applying the aqueous coating composition (1).

Comparative Example 4
A coating material was obtained in the same manner as in Example 1 except that the aqueous coating composition (1) was applied to the base material without applying the aqueous salt solution.

Reference example 1
Solvent type coating composition by mixing 30 parts of silicone resin SRX211 Paper Coating (manufactured by Toray Dow Corning, solid content 30%), 0.3 part of silicone resin SRX212P Catalyst (manufactured by Toray Dow Corning, curing catalyst) and 60 parts of toluene. Product was obtained (solid content 10%).
A glassine paper laminated with polyethylene (weighing 60 g / m ² ) was coated with a # 10 bar coater so that the concentration of the solvent-type coating composition was 0.6 g / m ^2, and then at 120 ° C. for 60 seconds. It dried and obtained the coating material (peeling material).

  The following evaluation was performed using the coating materials obtained from the above Examples and Comparative Examples. The evaluation results are shown in the following table.

Surface Condition Evaluation of Coating Material The coating layer surface of the coating material obtained from each example, comparative example and reference example was observed at a magnification of 600 times using a scanning electron microscope (SEM) and evaluated according to the following criteria.

A: Covered until the pulp fiber shape of the base material is almost concealed. ○: Although the pulp fiber shape of the base material is recognized, it can be confirmed that it is covered with a resin component. Pulp fiber shape is exposed and not covered with resin component

FIG. 1 is a photograph (600 ×) taken of the surface of the coating layer produced in Example 1 by scanning electron microscopy (SEM).
FIG. 2 is a photograph of the surface of paper, which is a base material used in Example 1, taken with an SEM (600 times).
FIG. 3 is a photograph taken with an SEM of the surface of the embodiment of Comparative Example 3 after application of the aqueous salt solution but without application of the aqueous coating composition (1) (600 times).
FIG. 4 is an aspect of Comparative Example 4 and is a photograph taken by SEM (600 magnifications) of the surface of the aqueous coating composition (1) coated on the base material without coating the aqueous salt solution.
FIG. 5 is a photograph of the surface of the coating layer obtained by painting the solvent-based coating composition of Reference Example 1 with an SEM (600 ×).

Evaluation of Coating Efficiency In the same manner as in each example or comparative example, a salt solution was applied to glassine paper as a base material and then dried in the same manner.
Using the # 12 bar coater, the aqueous coating composition was coated on the surface coated with the aqueous salt solution in the same manner as in the example or comparative example so that the solid content per surface of the substrate was 1 g / m ^2. Painted. Ten seconds after coating, moisture was blown off by air blow (discharge pressure 4 kg / m ² ).
Next, the coating layer was obtained by heating for 60 seconds in a hot air circulation drying oven at 120 ° C. to advance the drying and addition reaction. The mass of the obtained coating layer was measured.
The resin solid content mass of the painted aqueous coating composition was compared with the mass of the coating layer obtained as described above, calculated as mass% contributing to the formation of the coating layer, and evaluated according to the following criteria.

A: 70% or more of the solid resin mass of the painted aqueous coating composition contributes to the formation of the coating layer B: 40% or more of the solid resin mass of the painted aqueous coating composition to less than 70% Contributes to the formation of the coating layer. X: Less than 40% of the resin solid mass of the applied aqueous coating composition contributes to the formation of the coating layer.

Evaluation of degree of agglomeration of coating composition In the same manner as in each of the examples or comparative examples, a salt solution was applied to glassine paper as a base material and then dried in the same manner.
Using the # 12 bar coater, the aqueous coating composition was coated on the surface coated with the aqueous salt solution in the same manner as in the example or comparative example so that the solid content per surface of the substrate was 1 g / m ^2. Painted. Ten seconds after coating, moisture was blown off by air blow (discharge pressure 4 kg / m ² ), and the mass at this point was measured (a).
Next, the coating layer was obtained by heating for 60 seconds in a hot air circulation drying oven at 120 ° C. to advance the drying and addition reaction. The mass of the obtained coating layer was measured (b).
The mass change in the mass (a) after air blowing and the mass (b) of the obtained coating layer was calculated based on the following formula and evaluated according to the following criteria.
Mass change = (ab) / a * 100

A: Less than 30% by mass O: 30% by mass or more and less than 60% by mass X: 60% by mass or more

Peeling performance evaluation The peeling performance in the case where the coating materials obtained in Examples 1 to 7, 9 and Comparative Examples 1 and 2 and Reference Example 1 were used as a peeling material was evaluated.
An acrylic solvent-type pressure-sensitive adhesive (trade name BPS-5127, manufactured by Toyo Ink Co., Ltd.) was applied to the coating layer of each coating material, and heat-treated at 100 ° C. for 3 minutes. A high-quality paper of 64 g / m ² was bonded to the obtained adhesive-coated surface to prepare a sheet.
The obtained sheet was allowed to stand at 25 ° C. for 20 hours and then cut to a width of 5 cm to prepare an evaluation test piece.
About this test piece, the tensile tester was used, the fine paper was pulled at 180 degree angle on the conditions of peeling speed 0.3m / min, and the force (N) required for peeling was measured. Moreover, the case where peeling abnormality occurred was shown by x. The evaluation criteria are as follows.
In addition, since the coating material obtained in Example 8 is not a release material but a coated paper, this release performance evaluation is not performed.
Since the comparative example 3 has not painted the aqueous coating composition, this evaluation is not performed. In Comparative Example 4, this evaluation was not performed because a sufficient coating layer was not formed.

A: The force required for peeling is 0.01 N / 5 cm or more and less than 2.5 N / 5 cm. O: The force required for peeling is 2.5 N / 5 cm or more. X: Peeling abnormality such as tearing of the release material. Could not be measured

In all the examples, when water was blown off by air blow 10 seconds after the aqueous coating composition was applied, the resin solid content in the aqueous coating composition was sufficiently precipitated, and the coating layer was formed in a short time. The formation was confirmed.
In any of the coating materials obtained in the examples, it was confirmed that the substrate surface was coated with the resin component.
Comparative Example 1 is an example in which the amount of salt applied in the aqueous salt solution coating process is less than 0.3 g / m ² . In this example, precipitation of resin solids in the aqueous coating composition did not occur sufficiently, resulting in poor coating efficiency, and a coating layer was not sufficiently formed in a short time.
Comparative Example 2 is an example in which an aqueous resin solution was used instead of the aqueous salt solution. In this example, resin solids in the aqueous coating composition did not precipitate and the coating efficiency was poor, and the coating layer was not sufficiently formed in a short time.
Comparative Example 3 is an example in which only an aqueous salt solution is applied. A coating layer is not formed by painting only with an aqueous salt solution.
Comparative Example 4 is an example in which an aqueous coating composition was applied without applying an aqueous salt solution. In this example, the resin solid content in the aqueous coating composition did not sufficiently precipitate, and the aqueous coating composition was sucked into the substrate, so that the coating layer was not sufficiently formed in a short time.
Reference Example 1 is an example of a coating material (peeling material) obtained by applying a solvent-type coating composition to glassine paper laminated with polyethylene, and is a reference standard example.

  According to the production method of the present invention, even when the coating layer is formed on a substrate using an aqueous coating composition with reduced environmental load, a high production rate is possible and good manufacturability is obtained. There are industrial advantages.

Claims (8)

A method for producing a coating material having at least a substrate and a coating layer, the following steps:
A salt solution coating process for coating a salt solution on at least one surface of the substrate;
An aqueous coating composition coating step for further coating an aqueous coating composition on the surface of the aqueous salt solution coating, and a coating layer forming step for separating the water from the aqueous coating composition coating layer to form a coating layer;
Including
The aqueous coating composition includes one or more aqueous resin dispersions selected from resin emulsions, cationic dispersion resins and anionic dispersion resins, and the amount of salt applied in the salt aqueous solution coating step is , 0.3-10 g / m ² per surface area of the substrate,
Production method.   The manufacturing method of Claim 1 whose salt contained in the said salt aqueous solution is inorganic salt.   The production method according to claim 2, wherein the inorganic salt has one or more selected from the group consisting of sulfate ion, chloride ion, aluminum ion, iron ion, sodium ion and magnesium ion.   The production method according to claim 2 or 3, wherein the inorganic salt is one or more selected from the group consisting of aluminum sulfate, ammonium sulfate, aluminum chloride, sodium sulfate, magnesium chloride and magnesium sulfate.   The said salt aqueous solution is a manufacturing method in any one of Claims 1-4 which is an aqueous solution whose salt concentration is 0.5-40 mass%.   The aqueous coating composition comprises one or more aqueous resin dispersions selected from the group consisting of acrylic resin emulsions, acrylic silicone resin emulsions, silicone resin emulsions, epoxy resin dispersions and acrylic resin dispersions. Item 6. The production method according to any one of Items 1 to 5.   The manufacturing method according to claim 1, wherein the coating layer is a peelable coating layer, and the coating material is a release material. A method for producing a release material having at least a substrate and a peelable coating layer, the following steps:
Providing a substrate containing 1% by mass or more of a salt with respect to the mass of the substrate;
An aqueous coating composition coating step for coating the surface of the substrate with an aqueous coating composition; and a coating layer forming step for separating moisture from the aqueous coating composition coating layer to form a peelable coating layer;
Including
The aqueous coating composition comprises one or more aqueous resin dispersions selected from acrylic silicone resin emulsions and silicone resin emulsions,
The inorganic salt is one or more selected from the group consisting of aluminum sulfate, ammonium sulfate, aluminum chloride, sodium sulfate, magnesium chloride and magnesium sulfate,
Production method.

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