Silicone solution, manufacturing method thereof, water resistant / water repellent base material with use of the same and manufacturing process

Abstract

To provide a coating method that is a silicone solution application method without use of water and with use of microwave, and does not cause warping by application to a water absorptive pulp base material.SOLUTION: A manufacturing method for a silicone coating article, which is formed on a pulp base material by a surface treatment agent containing a silicon compound and a titanium compound that include a methyl group and a vinyl group, coats the base material in a process (1) in which the surface treatment agent is applied to the pulp base material, then, in a process (2) in which reaction of the surface treatment agent is advanced.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention is a method for applying a silicone solution using microwaves without using water, and does not cause warping of absorbent pulp substrates. Furthermore, the technology has extremely high water resistance and moisture resistance against water vapor, is low cost, and is highly safe for food, making it applicable to everyday items and food containers in addition to industrial products. [Background technology]

[0002] Conventionally, various coating materials have been developed and proposed for coating various articles such as food and beverages, medicines, cosmetics, detergents, miscellaneous goods, etc. Examples of such coating materials include metal deposition with aluminum foil or a deposition layer, and deposition of diamond-like carbon.

[0003] Metal deposition is an excellent barrier coating technology, but it has problems such as poor transparency due to the use of metal foil or a metal deposition layer, poor incineration suitability, and poor environmental friendliness, as waste disposal after use is not easy. Furthermore, vacuum coating has the disadvantage that it is not possible to apply a uniform coating to a three-dimensional shape.

[0004] In view of this, transparent barrier materials have been developed and proposed that have high barrier properties and also improve transparency and environmental friendliness (Patent Documents 1 and 2). The transparent barrier materials are made of a plastic material having a vapor-deposited film of a metal oxide such as silicon oxide or aluminum oxide on the surface of the plastic material.

[0005] In this case, it was considered that a barrier sheet in which a thin film of an inorganic oxide such as silicon oxide or aluminum oxide is coated on a plastic substrate is preferable. Even in transparent barrier materials having such a configuration, there are problems such as a decrease in adhesion between the substrate and the thin film of the inorganic oxide, a tendency for cracks to occur due to bending, and a decrease in barrier properties. In terms of barrier properties, although the barrier properties are significantly improved compared to a single plastic substrate, they are far from those of the above-mentioned aluminum foil, and there is a demand for even higher barrier properties that can fully meet the increasing demands for barrier properties.

[0006] In order to meet the requirements regarding barrier properties, a gas barrier laminate film has been proposed, which is characterized in that "on a substrate, a vapor-deposited layer made of an inorganic compound is used as a first layer, and a coating agent mainly composed of a water-soluble polymer and an aqueous solution containing at least one of (a) one or more alkoxides and / or hydrolysates thereof, or (b) tin chloride, or a water / alcohol mixed solution, is applied, and a gas barrier coating formed by heating and drying is laminated as a second layer" (Patent Document 3).

[0007] However, Patent Document 3 discloses laminating a barrier coating film on a vapor-deposited layer of an inorganic oxide. Although the barrier properties are improved by forming a multi-layered barrier layer, the density of the barrier coating film is not necessarily sufficient, the barrier properties are reduced under high temperature and high humidity conditions, and the water resistance and moisture resistance are not necessarily satisfactory.

[0008] In order to obtain excellent barrier properties, it is considered essential to prepare a barrier coating film with a dense film structure when forming a multi-layered barrier layer, and attempts have been made to form a barrier coating film using a sol-gel method. In order to form a dense coating film, it has been proposed to irradiate the barrier coating film with microwaves when forming the barrier coating film (Patent Document 4).

[0009] In recent years, from the viewpoint of carbon neutrality, etc., there is a growing demand to use biomass raw materials as substrates, replacing the use of plastics, which have been used as substrates, and methods of using them instead of paper, etc., while following the above-mentioned technology, have been proposed. For example, in coating paper using silicon compounds, it has been reported that by using a silicon atom with one of the four substituents that cannot be hydrolyzed, it is possible to coat paper and other fiber materials with the compound, thereby imparting appropriate strength, good light transmittance, water repellency, flexibility, and even abrasion resistance, etc. (Patent Document 5)

[0010] Furthermore, a method for producing a coated article including a silicone layer formed on the surface of a substrate by a surface treatment agent including a silicon compound or a titanium compound has been disclosed. It has been reported that a highly water-resistant and moisture-proof property against water vapor and the like can be imparted by a method for producing a coated article in which (1) a step of applying a surface treatment agent to the substrate surface, (2) a step of causing a chemical reaction on the substrate surface using water, and (3) a step of drying are carried out while moving the substrate (Patent Document 6). [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Special Publication No. 53-12953 [Patent Document 2] Japanese Patent Application Publication No. 179935 / 1983 [Patent Document 3] Patent No. 2790054 [Patent Document 4] JP 2010-000447 A [Patent Document 5] WО2020 / 149413 publication [Patent Document 6] JP 2023-046175 A Summary of the Invention [Problem to be solved by the invention]

[0012] Silicone coating is applied to highly hygroscopic substrates such as pulp to improve water repellency, but the conventional method generally uses water to promote the reaction of the silicone solution. However, although it is possible to improve water repellency, highly hygroscopic substrates such as pulp will warp due to the influence of water. The coating agent of the present invention has been developed to overcome the problems caused by the effects of moisture that occur during such reactions. By using no water whatsoever and applying a silicone coating using microwaves with adjusted power, it is possible to impart water repellency and water resistance to highly hygroscopic substrates such as pulp without warping. Furthermore, once a pulp substrate has warped, it becomes difficult to use it thereafter, but when the silicone coating of the present invention is applied, the warping improves and the substrate tends to return to its original flat shape. [Means for solving the problem]

[0013] A method for producing a silicone-coated article formed on a pulp substrate using a surface treatment agent containing a silicon compound containing methyl groups and vinyl groups and a titanium compound, comprising: (1) applying the surface treatment agent to a pulp substrate; (2) A step of promoting the reaction of the surface treatment agent The present invention relates to a method for producing a coating on a substrate.

[0014] The method is characterized in that the coating step is performed by a method selected from the group consisting of brush coating, spray coating, vacuum deposition, thermal evaporation, and spray coating of a mist created by ultrasonic waves.

[0015] The present invention relates to the above-mentioned production method, characterized in that in the step of promoting the reaction of the surface treatment agent, a method of infrared irradiation, hot air irradiation or microwave irradiation is used.

[0016] The present invention relates to a method for producing a coated article as described above, characterized in that in the coating step, coating of the substrate is carried out using a mobile conveying system.

[0017] The present invention relates to a method for producing the above-mentioned coated article, characterized in that the pulp substrate is paper, wood or a biodegradable material.

[0018] The present invention relates to a method for producing the above-mentioned coated article, characterized in that in the coating step, when the coating of the substrate is performed using a moving conveying system, a method for coating both sides simultaneously and a method for coating each side at a time are selected.

[0019] The surface treatment agent is characterized in that it contains a silane compound containing a methyl group and a vinyl group, and an alkoxytitanium compound.

[0020] The present invention relates to a surface treatment agent for forming a silicone layer on a substrate, which comprises a silane compound containing a methyl group and an alkoxytitanium compound.

[0021] The present invention relates to the above surface treatment agent, which is characterized in that the preparation of the surface treatment agent for forming a silicone layer on a substrate is carried out by stirring and mixing without using water or an organic solvent.

[0022] The alkoxytitanium compound is characterized in that the viscosity at 20°C is 0.1 to 200 mPa·s and the boiling point is 80 to 300°C. Effect of the Invention

[0023] In the present invention, the silicone-coated pulp substrate is free from warping and has water repellency and water resistance. In addition, silicone coating of a pulp substrate that has already warped can also improve the warping.

[0024] Furthermore, the manufacturing process according to the present invention is not only suitable for mass production, but also a technology that can be applied to everyday items and food containers in addition to industrial products due to its low cost and high safety for food, etc., and there is no risk of odor or discoloration.

[0025] Furthermore, the manufacturing process according to the present invention is not only suitable for mass production, but also a technology that can be applied to everyday items and food containers in addition to industrial products due to its low cost and high safety for food, etc., and there is no risk of odor or discoloration.

[0026] Furthermore, it has been found that the coating of the present invention penetrates into gaps due to its excellent permeability, even when there are microcavities or cracks on the surface or inside of the substrate, and fills the voids, thereby providing water resistance and also providing a repair effect. [Brief description of the drawings]

[0027] [Figure 1] General manufacturing process overview for the present invention [Diagram 2] Schematic diagram of an example of a manufacturing apparatus [Diagram 3] Pore ​​size of ultrasonic mist spray: (a) 5μm×780 pores / φ3.5mm (b) 10μm×150 pores / φ3.5mm [Figure 4] Schematic diagram of multiple ultrasonic mist generators arranged vertically DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] Figure 1 shows an overview of the manufacturing process for Example 1. The substrate is placed on a wire mesh conveyor made of fluororesin mesh and moves in the direction of the arrow. First, the surface treatment agent is sprayed from above and below. Next, excess surface treatment agent is blown off with air, and then water vapor is sprayed. The substrate is then dried with hot air. By using a fluororesin mesh on the conveyor, the surface treatment agent does not adhere to the substrate, and after drying with hot air, there is no adhesion film and the substrate can be used continuously in a clean state.

[0029] Figure 2 shows an overview of the manufacturing process involving air and liquid removal. The substrate is placed on a conveyor made of fluororesin or polyolefin (polyethylene or polypropylene) coated wire mesh, which moves in the direction of the arrow. First, the surface treatment agent is sprayed from above and below. Next, excess surface treatment agent is blown off with air, and then water vapor is sprayed. It is then dried with hot air. The use of fluororesin mesh on the conveyor prevents the surface treatment agent from adhering, and after drying with hot air, there is no film left behind and the substrate can be used continuously in a clean state.

[0030] Figure 3 shows a schematic diagram of an example of a manufacturing device. This example of a manufacturing device is composed of a substrate mounting position, a surface treatment chamber, a chemical removal chamber, a reaction chamber, a drying chamber, and a substrate removal position, and each chamber is connected by an interdiffusion prevention chamber. As shown in Figure 3, the fluororesin mesh conveyor is rotated by a transport roller and moves continuously. The substrate to be coated is placed on the conveyor at the substrate mounting position. Although not shown, the conveyor has some unevenness to prevent the substrate from moving.

[0031] The placed substrate passes through the mutual diffusion prevention chamber and enters the surface treatment chamber, where the surface treatment agent is sprayed evenly onto the substrate from above and below. It is referred to as a shower plate here, but in the case of a spray, it will be a multi-nozzle. In the case of a mist, the mist nozzle and supply method can be freely changed depending on the material. A device has been devised to prevent areas from being shaded by the mesh by applying slight vibrations to the conveyor. The mutual diffusion prevention chamber is designed to have minimum conductance according to the thickness of the substrate, and exhaust is emitted from the bottom.

[0032] The surface treatment chamber is made of aluminum metal, and the inside is coated with fluororesin. The walls of the treatment chamber are heated with a heater to prevent the surface treatment agent from being adsorbed. The bottom is equipped with equipment to collect any surface treatment agent that has flowed down. The substrate then enters the chemical solution removal chamber, where the excess chemical is blown off, leaving only the appropriate amount of coating. Like the surface treatment chamber, the chemical solution removal chamber is also equipped with equipment to collect any surface treatment agent that has flowed down at the bottom. Recovering and reusing as much chemical solution as possible reduces costs and prevents environmental pollution.

[0033] Next, in the reaction chamber, water vapor is sprayed from above and below to cause a reaction. The water vapor temperature is controlled at any temperature between room temperature and 100°C. Depending on the chemicals used, it can be made even higher. The temperature of the reaction chamber walls is kept at 100°C to 110°C to prevent water adsorption. A water collection facility is provided at the bottom. After sufficient reaction has occurred here, excess moisture is removed in a drying chamber, and the substrate is then removed by a robot at the substrate removal position. Depending on the size and shape of the substrate, it may fall directly into a box (not shown) placed earlier and be collected, rather than by the robot.

[0034] The conveyor continues to move downwards on rollers, then changes angle and returns. Using a rotating conveyor in this way makes it possible to simultaneously mix substrates of different sizes and shapes and perform film formation processing. Naturally, the length of each chamber is individually designed so that the substrates can stay there for the required time. The mutual diffusion prevention chamber between the chemical removal chamber and the reaction chamber is long to prevent water vapor and surface treatment agents from mixing, and exhaust is also performed from multiple points (not shown). When creating multiple layers, the surface treatment chamber and drying chamber are treated as one set, and multiple sets are installed in succession for the number of layers.

[0035] Figure 3 has been explained using an example of a single layer. Depending on the surface treatment agent, the reaction chamber may not be water vapor. An appropriate reaction atmosphere must be created. If an organic solvent removal reaction occurs, this can be dealt with by creating a treatment chamber behind the exhaust. Some processes require a long reaction time. In this case, the drying chamber in Figure 3 can be separated and placed on a separate conveyor, allowing for a long stay in the drying chamber. The equipment configuration shown in Figure 3 is merely one example of continuous processing, and does not necessarily have to be limited to a single conveyor.

[0036] The coating material produced by the production method of the present invention is made from an organosilicon compound or an organotitanium compound containing a methyl group and a vinyl group, and can form a coating layer by a sol-gel method or a method not depending on the sol-gel method. Furthermore, it exhibits excellent water repellency, water resistance, and moisture proofing properties.

[0037] [Silicon compounds] As the silicon compound, a metal alkoxysilane compound is mainly used. An example of the organosilicon compound used in the present invention is an organosilicon compound having a structure in which one or more methyl groups are bonded to a silicon atom. Such an organosilicon compound includes a compound represented by the following general formula (1). SiXn(CH3)4-n (1)

[0038] In formula (1), X independently represents an organic group, (CH3) represents a methyl group, and n is 1, 2, or 3. It is more preferable that n is 1 or 2. In other words, it is preferable that one molecule has one or two methyl groups. The organic group X is not particularly limited in the present invention, and specific examples thereof include an alkoxy group, an acyloxy group, an amino group, an isocyanate group, a hydroxy group, a hydrogen atom, and a halogen. Among these, an alkoxy group and a halogen are preferred. In the case of an alkoxy group, an alkoxy group with n=1 to 4 is preferred. Examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and a 2-methoxyethoxy group. In addition, multiple Xs in one molecule may be the same group or different groups.

[0039] Examples of the organosilicon compound represented by formula (1) for use in the present invention include trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, trimethylpropoxysilane, dimethyldipropoxysilane, methyltripropoxysilane, trimethylbutoxysilane, dimethyldibutoxysilane, methyltributoxysilane, trimethylpentoxysilane, dimethyldipentoxysilane, methyltripentoxysilane, dimethyldiphenylsilane, methyldiphenylsilane, dimethyldiphenylsilane, methyldiphenyl(ethynyl)silane, and the like. )silane, fluoro(methyl)diphenylsilane, [tris(dimethylmethoxysilyl)methyl]diphenylsilane, ethoxy(methyl)diphenylsilane, diethoxydiphenylsilane, trimethylstannylmethyldiphenylsilane, chloro-N,N-dimethyldiphenylsilaneamine, azido(methyl)diphenylsilane, N,N,N',N'-tetramethyldiphenylsilanediamine, dimethyldiphenylsilane, diphenylmethylchlorosilane, dianilinodimethyldiphenylsilane, (1-fluorovinyl)methyldiphenylsilane, methyltriphenylsilane, and the like, but are not limited thereto. Among these, alkoxysilanes are particularly preferred, and trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, and methyltriethoxysilane are more preferred.

[0040] Further, examples of the organosilicon compound used in the present invention include organosilicon compounds having a structure in which one or more vinyl groups are bonded to a silicon atom. Examples of such organosilicon compounds include compounds represented by the following general formula (2). (CH2=CH)n-Si-(OR)4-m ···(2)

[0041] In formula (2), CH2=CH represents a vinyl group, and OR represents an alkoxy group. n is 1 or 2. m is also 1 or 2. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a 2-methoxyethoxy group, etc. In addition, a plurality of (OR) in one molecule may be the same alkoxy group or different alkoxy groups.

[0042] Examples of the organosilicon compound represented by formula (2) used in the present invention include, but are not limited to, vinyltrimethoxysilane, divinyldimethoxysilane, vinyltrimethoxysilane, divinyldiethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, divinyldipropoxysilane, vinyltributoxysilane, divinyldibutoxysilane, vinyltripentoxysilane, divinyldipentoxysilane, vinyltriphenoxysilane, divinyldiphenoxysilane, vinyldimethoxyethoxysilane, and divinylmethoxydiethoxysilane. Among these, vinyltrimethoxysilane, divinyldimethoxysilane, vinyltrimethoxysilane, divinyldiethoxysilane, and vinyltriethoxysilane are more preferable.

[0043] [Siloxane compounds] Siloxane compounds may also be used in the present invention, such as 1,1,3,3-tetramethyl-1,3-diethoxypropanedisiloxane, diethoxypolydimethylsiloxane, and 3,3-diethoxy-1,1,1,5,5,5-hexamethylpentanetrisiloxane.

[0044] Examples of other siloxane compounds that can be used in the present invention include organopolysiloxanes, such as the compound shown in formula 3. (R3O)aR43-aSiO-(SiR5R6O)m-Si(R7O)bR83-b (Formula 3)

[0045] Here, R3 and R7 are each independently an alkyl group having 1 to 3 carbon atoms, R4 and R8 are each independently a functional group selected from an alkyl group having 1 to 6 carbon atoms, a haloalkyl group, and an allyl group, R5 and R6 are each independently an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, a and b are each independently an integer of 1 to 3, preferably 2 or 3, and m is an integer of 10 to 1500. For example, the component (formula 3) can be prepared by subjecting a both-terminal hydroxy-modified organopolysiloxane (silicone oil) represented by HO-(SiR5R6O)mH, whose degree of polymerization or average molecular weight is known, to a hydrolysis and condensation reaction with an alkylalkoxysilane compound having 2 to 4 hydrolyzable groups corresponding to R3O and R7O and 0 to 3 alkyl groups corresponding to R4 and R8, where the total of the hydrolyzable groups and the alkyl groups is 4. Here, when the alkylalkoxysilane compound has two hydrolyzable groups and two alkyl groups, the value of a in the obtained component (Formula 3) is 1, and when the alkylalkoxysilane compound has four hydrolyzable groups, the value of a in the same component (Formula 3) is 3.

[0046] More preferably, in the component (Formula 3), R3 and R7 at both ends of the molecular chain are each independently an alkyl group selected from a methyl group and an ethyl group, R4 and R8 are each independently an alkyl group selected from a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group, R5 and R6 are each independently a hydrocarbon group selected from a methyl group, an ethyl group, and a phenyl group, a and b are each independently an integer of 2 or 3, and m is a compound having a structure in the range of 25 to 1250. The viscosity is also preferably in the range of 100 to 100,000 mPa·s, more preferably in the range of 250 to 50,000 mPa·s, and even more preferably in the range of 500 to 30,000 mPa·s. If the viscosity is less than 100 mPa·s, the water repellency of the coating layer decreases. On the other hand, if it exceeds 100,000 mPa·s, the workability during the formation of the coating layer decreases, and there is a risk of the water slipping property also decreasing. The viscosity referred to here is a value measured by a measurement method in accordance with JIS Z 8803 (EHD type viscometer, 25°C for 1 minute, manufactured by Toki Sangyo Co., Ltd.).

[0047] The siloxane compound used in the present invention is preferably a mixture having a vapor pressure of 800 Pa or less at 25° C. More preferably, the vapor pressure at 25° C. is 600 Pa or less, and particularly preferably, the vapor pressure at 25° C. is 300 Pa or less. The above ranges are preferred from the viewpoint of ease of application and spraying in the present invention.

[0048] The siloxane compound used in the present invention preferably has a boiling point of 40 to 300° C., more preferably has a boiling point of 50 to 250° C., and particularly preferably has a boiling point of 60 to 220° C. These are also preferred from the viewpoint of coating, spraying, etc., such as ease of thermal reaction.

[0049] [Cyclic siloxane compounds] In the present invention, cyclic siloxane compounds can also be used. Cyclic siloxanes are siloxanes with a ring structure that have a dimethylsiloxane unit (CH3)2Si-O-, in which a silicon atom (Si) with two methyl groups on the silicon atom is bonded to an oxygen (O) atom, and are used as raw materials for manufacturing silicone products. Among them, the most common cyclic siloxanes are D4, D5, and D6. Octamethylcyclotetrasiloxane, commonly known as D4, is a cyclic siloxane containing four dimethylsiloxane units (CH3)2Si-O-. Decamethylcyclopentasiloxane, commonly known as D5, is a cyclic siloxane containing five dimethylsiloxane units (CH3)2Si-O-. Dodecamethylcyclohexasiloxane, commonly known as D6, is a cyclic siloxane containing six dimethylsiloxane units (CH3)2Si-O-. These siloxane compounds can be used alone or in combination, but the most common method of use is to use them in combination with an alkoxysilane to form a composite. For food containers, etc., it is preferable to use D5.

[0050] [catalyst] The catalyst used in the present invention may be an acid, an amine, an organometallic, etc. In the case of an organometallic, it is an organotin compound or a titanium-based chelate compound, but from the viewpoint of safety, a titanium-based catalyst is preferred. Specifically, diisopropoxytitanium bis(acetylacetonate), titanium tetra(acetylacetonate), dioctanoxytitanium dioctanate, diisopropoxytitanium bis(ethylacetoacetate), titanium methoxide, titanium ethoxide, titanium propoxide, titanium butoxide, etc. can be used, and these may be used in combination. In particular, it is preferable to use titanium methoxide, titanium ethoxide, titanium propoxide, or titanium butoxide.

[0051] In some cases, a silane coupling agent may be used. Specifically, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Methyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane lan, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris-(trimethoxysilylpropyl)isocyanurate 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and the like. These catalysts and coupling agents may be used in mixture, or may be used alone or in combination of a plurality of them.

[0052] [Coating method] Coating of the substrate can be performed by a variety of methods, including brushing, spraying, dipping, roll coating, spin coating, and printing. A coating film of the desired dry thickness can be formed by one coat, and it can also be overcoated 2 to 5 times. When overcoating, a heating and drying treatment can be performed after each coat. A particular key point of the present invention is that water is not added to the reaction system. Conventional methods have promoted reactions by spraying water after applying a silicone solution, but the present invention promotes the reaction without adding excess water.

[0053] For this reason, microwave irradiation has the effect of promoting the reaction, but it is important to keep in mind that the microwave power output should be kept low when irradiating. Increasing the microwave output makes it easier to promote the reaction, but on the other hand, it is more likely to generate heat, and the substrate to be coated, especially materials that are prone to warping due to heat such as pulp substrates, will warp significantly. For this reason, it is necessary to reduce the microwave output and irradiate at a low output that minimizes heat generation. Specifically, irradiation is performed at 500 W or less for 1 minute or less, preferably at 300 W or less for 1 minute or less, and more preferably at 150 W or less for 1 minute or less.

[0054] The procedure for coating a substrate is as follows: first, the substrate is coated with a silicone compound to form a coating film.

[0055] [Warping of the base material] If the substrate is subjected to coating and warps significantly, that is, if the dimensional stability is poor, this is undesirable because it will cause problems when the product is used. The warpage value is preferably 1.0 mm (1.0%) or less per 100 mm of the base material.

[0056] For this reason, it is necessary to control the temperature, application amount, and humidity during the processes of conditioning the substrate before coating, applying the reaction treatment agent and reaction accelerator, and drying. Generally, if the substrate is susceptible to water, such as paper or pulp, it is best to keep the humidity of the substrate before coating at 60-10%. In particular, moisture has the effect of promoting the reaction of silicone coating, so controlling the moisture content is important. However, in the case of the present invention, even moisture in the air is enough to promote the reaction, so the need for humidity control before coating can be largely eliminated.

[0057] [Preprocessing] Some substrates are difficult to silicone coat on the surface, so pretreatment may be required before silicone coating. The substrate can be subjected to physical or chemical treatments such as corona discharge treatment, ozone treatment, atmospheric pressure low-temperature plasma treatment using oxygen gas, nitrogen gas, hydrogen gas, etc., plasma treatment in a hydrogen atmosphere or Ar atmosphere in a vacuum chamber, glow discharge treatment, chemicals, high-temperature water vapor, etc., or pretreatments such as a primer coating layer, an undercoat layer, an anchor coating layer, an adhesive layer, a vapor-deposited anchor coating layer, etc., to improve adhesion. Surface cleaning with alcohol can also be used to create hydrophilicity.

[0058] [Transportation method] In the present invention, since the silicone coating of the substrate is aimed at high speed and mass production, when spraying both sides at the same time, it is desirable to use a mesh-like carrier as shown in Figure 1 as a conveyor-type carrier for the substrate. There are no particular restrictions on the size of the mesh as long as there is no unevenness in the transportation of the substrate and the coating. However, to prevent unevenness, a slight vibration is given to the carrier so that there are no uncoated areas on the mesh on the carrier. Methods of vibration include mechanical vibration and ultrasonic vibration.

[0059] There is no particular limitation on the shape of the mesh, and circles, rectangles, hexagons, and other polygonal shapes are used. A polygonal shape such as a hexagon is preferable to ensure even coating. Furthermore, it is preferable to have projections and recesses that match the substrate so that the substrate does not fall off. The material of the mesh is preferably one that can withstand the high temperatures that occur during drying, and is also preferably chemically resistant since the material contains organic chemicals.

[0060] When the material is an inorganic compound, examples include metals, ceramics, and carbon fibers. In particular, in the case of metals, steel, stainless steel, aluminum, magnesium, titanium, copper, lead, zinc, nickel, chromium, tungsten, gold, silver, platinum, and alloys can be used.

[0061] When the material is a polymer, it is polyethylene, polypropylene, or fluororesin. From the viewpoint of heat resistance, fluororesin is preferable, and from the viewpoint of cost, polypropylene is preferable. Specific examples include polyolefins, particularly polyethylene, polypropylene, and ethylene vinyl acetate, as well as fluorine-containing compounds (fluorine resins), such as polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE, CTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), and ethylene-chlorotrifluoroethylene copolymer (ECTFE). When a mesh-shaped material is produced from these resins, they may be used by coating the above-mentioned metallic material.

[0062] When irradiating microwaves to the substrate during transport or in the stocker, there is a risk of abnormal discharge or fire, so it is desirable to avoid metal or graphite as the material for the mesh-shaped carrier in the relevant area and use a polymer material.

[0063] [How to recover substrate material] After silicone coating is completed, if the substrate is in the form of a film or sheet, a roll-to-roll drum winding system can be used.

[0064] [Other methods for recovering substrate materials] In addition, when the substrate is a non-flexible substrate, a winding method using a caterpillar can be used.

[0065] [Spray form] In the present invention, when coating a substrate with silicone, the aim is to achieve high speed and mass production, so when spraying both sides simultaneously, it is desirable to use a mesh-like carrier as a conveyor-type carrier for the substrate. There are no particular restrictions on the size of the mesh as long as there is no unevenness in the transportation of the substrate and the coating. However, to prevent unevenness, a slight vibration is given to the carrier so that there are no uncoated areas on the carrier. Methods of vibration include mechanical vibration and ultrasonic vibration.

[0066] The vibration may be applied by mechanically applying a slight impact intermittently to the conveyor or substrate, or by intermittently blowing a part of the raw material gas, carrier gas, or auxiliary gas onto the back surface of the substrate. When gas is blown directly onto the substrate, if the distance between the substrate and the raw material supply nozzle, shower plate, or ceiling of the processing chamber is longer than the short side of the substrate, it is desirable to provide a guide, guard, or stopper to hold the substrate in the processing chamber so that the substrate does not flip over or move excessively due to wind pressure. It is desirable to have gaps between the guide, guard, stopper and base material so that they do not come into contact with each other unless strong wind pressure is generated.

[0067] There is no particular limitation on the shape of the mesh, and circles, rectangles, hexagons, and other polygonal shapes are used. A polygonal shape such as a hexagon is preferable to ensure even coating. The material of the mesh is preferably one that can withstand the high temperatures that occur during drying, and is also preferably chemically resistant since the material contains organic chemicals. Specifically, polyethylene, polypropylene, and fluororesin are used. From the viewpoint of heat resistance, fluororesin is preferable, and from the viewpoint of cost, polypropylene is preferable.

[0068] [Shower plate] When supplying material by spray supply or mist spraying, if the substrate (sheet-shaped or three-dimensional workpiece) is large or multiple substrates are coated simultaneously for mass production, the uniformity of film thickness caused by the supply of raw material at the center and ends of the conveyor becomes an issue depending on the distance from the nozzle.

[0069] To address this issue (1) An air shower type nozzle with many small holes in a pipe is positioned at an angle to the running direction of the wire mesh conveyor. (2) A shower plate having a large number of pores arranged parallel to the substrate is disposed. (3) Install correction components such as baffles, slits, and shutters to make the gas distribution uniform at the center and ends of the conveyor. (4) A fan (agitation blade) is installed between the nozzle and the substrate in the coating chamber to uniformly distribute the gas at the center and ends of the conveyor. Such a gas distribution uniformity measure is effective.

[0070] In the case of double-sided coating, the gas distribution equalization means (1) to (4) are provided on both sides of the substrate. However, in cases where the material gas flows around to the back side of the substrate due to the gas residence time in the chamber and the arrangement of the substrates on the mesh conveyor, the gas distribution equalization means (1) to (4) may be provided on only one side. In addition, (1) the pipe of the air shower type nozzle having many fine holes is not limited to a straight pipe, but may be a curved pipe as long as it can efficiently supply the raw material gas to the end of the conveyor. For the same reason as in (1), (2) the shower plate is not limited to a flat type, but may be a curved type.

[0071] [Focused coating on hinges and joints] When the substrate is not flat or planar, but has a three-dimensional shape and has hinges, joints, and other portions that are subjected to loads such as bending and sliding, the film thickness must be thicker than that of the flat portions. In this case, apart from the uniformity of the coating distribution in the center and ends of the conveyor, the hinges and joints will be coated intensively. (1) In addition to the air shower nozzle and shower plate described above, a nozzle for supplying coating material is arranged facing the key area. (2) Adjust the aperture ratio per unit area of ​​the air shower nozzle or shower plate. (3) Adjusting the shape of compensation components such as baffles, slits, and shutters. Such a correction is effective.

[0072] [Backside coating with single-sided supply by pillar] The areas where the wire mesh of the wire mesh conveyor comes into contact with the substrate are masked, resulting in insufficient coating. We have previously disclosed a method of applying slight vibrations to the carrier, but uneven coating can be improved by making the wire mesh conveyor that comes into contact with the substrate a point contact rather than a surface contact. By using pillars (thin supports) for point contact, the raw material vapor (mist) can pass through the gaps in the pillars to get to the back side of the substrate. Therefore, if the raw material mist concentration distribution in the coating chamber is uniform and the residence time is long, the raw material nozzles can be placed on only one side of the conveyor. The length of the pillars (thin supports) is determined appropriately based on the area of ​​the substrate, the gap in the wire mesh conveyor, the mist particle size, the carrier gas, and the pressure in the processing chamber. The longer the pillars (thin supports), the better; however, due to conveyor restrictions, it is best to keep the length to 1 / 2 to 1 / 10 of the short side of the substrate. Small mist particle size is desirable for backside coating because it provides a longer residence time.

[0073] [Process bulkhead] The processing space of each continuous process using a moving conveyor or other conveyor is separated by a partition, but since there is a gap through which the base material (thick work, sheet, film) passes, the partition does not need to be completely airtight. Therefore, O-rings and metal gaskets are not required, but the closer the gap is to the thickness of the base material to prevent gases from mixing between each process, the better.

[0074] [Airtight bulkhead] If there is a process that takes longer than the other processes among the consecutive processes, it is desirable to separate the process room (chamber) with a movable partition by using a moving transport device such as a conveyor. In this case, too, if the pressure difference with the adjacent process is small, O-ring seals or gasket seals are not required.

[0075] [Decompression and vacuum processing] In processes such as drying, degassing, and dehydration (esterification), temperature and pressure affect reaction time, so vacuum processes such as reducing pressure may be effective, but it is also possible to replace continuous transport with intermittent transport and perform batch processing in an airtight processing chamber so that there is no pressure difference with other adjacent processes. In particular, in the case of heat treatment, high airtightness has the advantage of less impact on other adjacent processes.

[0076] [Conveyor running speed] If the processing time for each process is different, (1) A mobile transport device such as a conveyor is integrated, and the processing time is adjusted according to the length of the processing chamber. (2) Separate moving transport devices such as conveyors into each process and adjust the conveyor speed. (3) Batch processing, in which a moving transport device such as a conveyor is divided into each process, the conveyor runs intermittently rather than at a constant speed, and each process is considered to be processed separately for a fixed period of time. is selected from.

[0077] [Airtight bulkhead for maintenance] If there is a process that requires periodic maintenance, it is preferable for the movable partition to be sealed with an airtight seal such as an O-ring or gasket.

[0078] [Double partition with exhaust mechanism] In order to prevent the gaseous and misty coating materials from mixing between the processes, it is desirable to use a double partition with an exhaust mechanism such as a vacuum pump, and depending on the raw material gas, it is treated with waste gas such as a mist trap, scrubber, or adsorption tower. In addition, to prevent pressure differences from occurring between the process chambers due to the reduction in pressure by the vacuum pump, it is desirable to install a conductance valve, butterfly valve, or gate valve linked to a pressure gauge between the suction port in the double partition and the vacuum pump.

[0079] [Air curtains in bulkheads] In order to prevent the raw materials from mixing between processes and to extend the residence time of the raw material mist, it is desirable to prevent turbulence by directing inert auxiliary gas such as nitrogen or argon toward the exhaust port of the partition. An air curtain with an array of fine blowing holes is desirable to create a laminar flow at the opening of the partition with a small amount of auxiliary gas flow.

[0080] [Mist particle size control] If the base material has a rough surface, or is a fibrous material such as pulp, and the raw material is applied with a spray bottle, the mist particle size will be larger than the fine pore size of the material, resulting in insufficient coating, so it is necessary to supply the raw material in the form of a mist with a particle size smaller than the gaps between the fibers using a mist generator such as ultrasonic waves. Also, if the mist particle size is small, the mist will remain in the treatment chamber for a longer time, which has the advantage of reducing unreacted raw material and increasing coating efficiency. Conversely, if the particle size is large, the mist particles turn into droplets on the substrate surface, causing inconvenience to the reaction, so it is desirable that the mist particle size is small and uniform. At atmospheric pressure, large particle size mist does not remain in the space and tends to fall freely due to gravity. Taking advantage of this property, large particle size mist can be removed by installing an S-tube, U-tube, or spiral tube mist trap between the ultrasonic mist generator and the base material.

[0081] [Ultrasonic mist particle size control] The mist particle size can be changed by changing the pore size of the doughnut-shaped ultrasonic transducer, but if the pore size is too small, it becomes difficult to spray mist from viscous fluids such as polymers, and this can cause clogging. The pore size of the ultrasonic transducer is shown in Fig. 3. (a) shows the pore size of 5μm×780 pores / φ3.5mm for a commercially available water vapor humidifier (5VDC 110kHz). (b) is a 10 μm × 150 pores / φ3.5 mm for spraying silicone chemicals. When the silicone liquid was sprayed, (a) generated a strong mist immediately after spraying, but it became clogged over time, while (b) sprayed a stable mist for a long period of time.

[0082] [Ultrasonic mist spraying up and down] In the case of the doughnut-shaped multi-hole ultrasonic transducer, mist can be sprayed by sucking up the chemical liquid or dropping droplets from above, so the direction of mist irradiation does not matter. Figure 4 is a schematic diagram of a shower panel with many ultrasonic transducers arranged vertically and horizontally. By arranging the panels vertically and horizontally and passing the substrate through the inside, double-sided film formation is possible, increasing the density of the chemical mist and improving productivity. The figure shows two directions, top and bottom, but by covering the entire film formation chamber from top, bottom, left and right in the direction of the substrate's movement, it has the effect of recovering unreacted chemical liquid, reducing the amount of chemical liquid consumed, simplifying the device configuration, and reducing the exhaust load. In air spray type spraying, the internal pressure of the reaction chamber increases because a compressor sends carrier gas into the reaction chamber, but ultrasonic mist spraying is a closed system. EXAMPLES

[0083] The present invention will be specifically described below by showing examples, but the present invention is not limited by these examples, and various applications are possible within the scope of the technical scope of the present invention. Each example and each comparative example were measured and evaluated by the methods shown below.

[0084] (1) Measurement of initial water droplet contact angle (water repellency test) Using a contact angle meter of CA-DT type manufactured by Kyowa Interface Science Co., Ltd., a 2 μL water droplet was dropped onto the water-repellent film of the sample silicone in the air (about 25° C.) to measure the static contact angle of the water droplet. A contact angle of 90° or less was judged to be hydrophilic, and a contact angle of 90° or more was judged to be water-repellent.

[0085] (2)Water resistance test After the coating process, colored water was dripped onto the surface of the substrate, and a sheet of white copy paper was placed underneath the substrate. The water that disappeared was constantly replenished, and if no stains were found on the copy paper after 24 hours, it was determined that the substrate was water resistant.

[0086] (3) Alcohol resistance test After the coating process, colored alcohol was dripped onto the surface of the substrate, and a sheet of white copy paper was placed on the bottom of the substrate. The alcohol that disappeared was constantly replenished, and if there was no stain on the copy paper after 24 hours, it was judged to have alcohol resistance.

[0087] (4) Warping of the substrate In order to measure the distortion effect on the substrate after coating, the degree of warping was measured in accordance with JIS0621-1984. For a 100 mm test piece, a warp height of 1.0 mm or less was considered to have passed the test.

[0088] (5) Check for the presence of powder on the surface In order to check whether or not any substances (e.g., powder) that did not adhere to the surface of the substrate were generated after the coating process, black vinyl tape was applied, and then the tape was peeled off and visually checked whether or not any white substances were attached to the adhesive surface. If any white substances were observed, it was marked as ×, and if no adhesion was observed, it was marked as ○.

[0089] (Example 1-1) One-coat process A reaction liquid was prepared by mixing 50 ml of methyltrimethoxysilane (MTMS, manufactured by Aldrich), 50 ml of vinyltrimethoxysilane (VTMS) and 5 ml of tetrapropoxytitanium in a 500 ml beaker with stirring at a temperature of 20° C. for 5 minutes. The prepared reaction solution was simultaneously applied to both sides of a pulp substrate (paper entrance) with a thickness of 0.7 mm and a length and width of 10 cm, which had been previously conditioned at room temperature in a desiccator with a humidity of 25%. The coated paper entrance was then placed in a household microwave oven (Panasonic, NE-NS301) and irradiated with microwaves at 150 W for 1 minute. After coating, the cardboard was left at room temperature for 24 hours, and then the water repellency, water resistance, warping, and the presence or absence of surface powder were measured.

[0090] (Example 1-2) One-coat process A reaction liquid was prepared by mixing 50 ml of methyltrimethoxysilane (MTMS), 50 ml of vinyltrimethoxysilane (VTMS), 5 ml of tetrapropoxytitanium, 5 ml of decamethylcyclopentasiloxane (D5), and 5 ml of tetrapropoxytitanium in a 500 ml beaker at 20°C for 5 minutes with stirring. The prepared reaction solution was simultaneously applied to both sides of a pulp substrate (paper entrance) with a thickness of 0.7 mm and a length and width of 10 cm, which had been previously conditioned at room temperature in a desiccator with a humidity of 25%. The coated paper entrance was then placed in a household microwave oven (Panasonic, NE-NS301) and irradiated with microwaves at 150 W for 1 minute. After coating, the cardboard was left at room temperature for 24 hours, and then the water repellency, water resistance, warping, and the presence or absence of surface powder were measured.

[0091] (Example 1-3) One-coat process A reaction liquid was prepared by mixing 50 ml of methyltrimethoxysilane (MTMS), 25 ml of vinyltrimethoxysilane (VTMS), 25 ml of decamethylcyclopentasiloxane (D5), and 5 ml of tetrapropoxytitanium in a 500 ml beaker with stirring at a temperature of 20° C. for 5 minutes. The prepared reaction solution was simultaneously applied to both sides of a pulp substrate (paper entrance) with a thickness of 0.7 mm and a length and width of 10 cm, which had been previously conditioned at room temperature in a desiccator with a humidity of 25%. The coated paper entrance was then placed in a household microwave oven (Panasonic, NE-NS301) and irradiated with microwaves at 150 W for 1 minute. After coating, the cardboard was left at room temperature for 24 hours, and then the water repellency, water resistance, warping, and the presence or absence of surface powder were measured.

[0092] (Example 1-4) One-coat process A reaction liquid was prepared by mixing 25 ml of methyltrimethoxysilane (MTMS), 50 ml of vinyltrimethoxysilane (VTMS), 5 ml of decamethylcyclopentasiloxane (D5), and 5 ml of tetrapropoxytitanium in a 500 ml beaker with stirring at a temperature of 20° C. for 5 minutes. The prepared reaction solution was simultaneously applied to both sides of a pulp substrate (paper entrance) with a thickness of 0.7 mm and a length and width of 10 cm, which had been previously conditioned at room temperature in a desiccator with a humidity of 25%. The coated paper entrance was then placed in a household microwave oven (Panasonic, NE-NS301) and irradiated with microwaves at 150 W for 1 minute. After coating, the cardboard was left at room temperature for 24 hours, and then the water repellency, water resistance, warping, and the presence or absence of surface powder were measured.

[0093] (Example 2-1) Two-coating process Reaction solution 1 was prepared by mixing 50 ml of methyltrimethoxysilane (MTMS), 50 ml of vinyltrimethoxysilane (VTMS), and 5 ml of tetrapropoxytitanium in a 500 ml beaker with stirring at a temperature of 20° C. for 5 minutes. Next, 50 ml of methyltrimethoxysilane (MTMS), 5 ml of decamethylcyclopentasiloxane (D5), and 5 ml of tetrapropoxytitanium were mixed in a separate 500 ml beaker with stirring at a temperature of 20° C. for 5 minutes to prepare reaction solution 2. The prepared reaction solution 1 was simultaneously applied to the front and back of a pulp substrate (paper entrance) with a thickness of 0.7 mm and a length and width of 10 cm, which had been previously conditioned at room temperature in a desiccator with a humidity of 25%. The coated paper entrance was then placed in a household microwave oven (Panasonic, NE-NS301) and irradiated with microwaves at 150 W for 1 minute. Five minutes after the irradiation, the thick paper was further spray-coated on both sides simultaneously with reaction liquid 2. The coated paper entrance was then placed in a household microwave oven (NE-NS301, manufactured by Panasonic) and irradiated with microwaves at 150 W for one minute. After leaving it at room temperature for 24 hours, the water repellency, water resistance, warping and the presence or absence of surface powder were measured.

[0094] (Example 2-2) Two-coating process The reaction solution 2 prepared in Example 2-1 was simultaneously applied to both sides of a pulp substrate (paper entrance) having a thickness of 0.7 mm and a length and width of 10 cm, which had been previously conditioned at room temperature in a desiccator with a humidity of 25% by spray coating. The coated paper entrance was then placed in a household microwave oven (NE-NS301, manufactured by Panasonic) and irradiated with microwaves at 150 W for 1 minute. Five minutes after the irradiation, the thick paper was further spray-coated with the reaction solution 1 prepared in Example 2-1 on both sides at the same time. The coated paper entrance was then placed in a household microwave oven (NE-NS301, manufactured by Panasonic) and irradiated with microwaves at 150 W for one minute. After leaving it at room temperature for 24 hours, the water repellency, water resistance, warping and the presence or absence of surface powder were measured.

[0095] (Comparative Example 1) Reaction acceleration by water The pulp substrate was previously conditioned for one week in a desiccator at room temperature with a humidity of 25%. Next, the reaction solution prepared in Example 1-1 was spray-coated on the paper entrance simultaneously on both sides, and then water was spray-coated at room temperature to cause a reaction. Thereafter, the coating was allowed to dry naturally, and the resulting silicone coating was evaluated in the same manner as in the Examples.

[0096] (Comparative Example 2) Reaction acceleration by water The pulp substrate was previously conditioned for one week in a desiccator at room temperature with a humidity of 25%. Next, the reaction solution prepared in Example 1-3 was spray-coated on the paper entrance simultaneously on both sides, and then water was spray-coated at room temperature to cause a reaction.

[0097] (Comparative Example 3) Reaction acceleration by water The pulp substrate was previously conditioned for one week in a desiccator at room temperature with a humidity of 25%. Next, the reaction solution prepared in Example 2-1 was spray-coated on the paper entrance simultaneously on both sides, and then water was spray-coated at room temperature to cause a reaction.

[0098] (Comparative Example 4) Reaction promotion by microwaves The reaction solution prepared in Example 1-1 was simultaneously applied to both sides of a pulp substrate (paper entrance) having a thickness of 0.7 mm and a length and width of 10 cm, which had been previously conditioned at room temperature in a desiccator with a humidity of 25% by spray coating. The coated paper entrance was then placed in a household microwave oven (NE-NS301, manufactured by Panasonic) and irradiated with microwaves at 750 W for 1 minute.

[0099] (Comparative Example 5) Reaction promotion by microwaves The reaction solution prepared in Example 2-1 was simultaneously applied to both sides of a pulp substrate (paper entrance) with a thickness of 0.7 mm and a length and width of 10 cm, which had been previously conditioned at room temperature in a desiccator with a humidity of 25% by spray coating. The coated paper entrance was then placed in a household microwave oven (NE-NS301, manufactured by Panasonic) and irradiated with microwaves at 750 W for 1 minute.

[0100] The experimental results are shown in Table 1. [Table 1] [Industrial Applicability]

[0101] According to the present invention, it is possible to obtain a silicone-coated pulp substrate with good water repellency in a short time, even if the substrate has a complex shape. In addition, there is almost no warping or distortion of the substrate after drying, and there is little damage to the product. There is also no coloring or odor. [Explanation of symbols]

[0102] 1. Wire mesh conveyor 2 Base material 3. Mist Generator 4 Nozzles 5 Movable bulkhead 6 Vacuum Exhaust Pump 7. Pressure Gauge 8 Conductance Valve 9. Infrared Heater 10 Temperature adjustment slit 11 Infrared Temperature Monitor 12 Heater window purge shower plate 13 Micro-vibration generator 14 Substrate recovery sorter 15 Stepping motor 16 Surveillance Monitor 17 Delivery drum 18 Winding drum 19 Biodegradable flexible film 20 Rolled non-flexible substrate

Claims

1. A method for producing a silicone-coated article formed on a pulp substrate using a surface treatment agent containing a silicon compound containing methyl groups and vinyl groups and a titanium compound, comprising: (1) applying the surface treatment agent to a pulp substrate; (2) A step of promoting the reaction of the surface treatment agent A manufacturing method for coating a substrate.

2. 2. The method according to claim 1, wherein the coating step is a method selected from the group consisting of brush coating, spray coating, vacuum deposition, thermal evaporation, and ultrasonic mist spray coating.

3. 3. The method according to claim 1, wherein the step of promoting the reaction of the surface treatment agent involves the use of a method involving infrared irradiation, hot air irradiation or microwave irradiation.

4. 4. The method for producing a coated article according to claim 1, wherein in the coating step, the substrate is coated using a moving conveying system.

5. 5. The method for producing a coated article according to claim 1, wherein the pulp substrate is paper, wood or a biodegradable material.

6. 6. The method for producing a coated article according to claim 1, wherein the coating step is performed by a mobile conveying system, and the method is selected from a method of simultaneously coating both sides of the substrate, and a method of coating each side of the substrate.

7. 2. The compound according to claim 1, wherein the surface treatment agent comprises a silane compound containing a methyl group and a vinyl group, and an alkoxytitanium compound.

8. A surface treatment agent for forming a silicone layer on a substrate, comprising a silane compound containing a methyl group and an alkoxytitanium compound.

9. 2. The surface treatment agent according to claim 1, wherein the surface treatment agent for forming a silicone layer on a substrate is prepared by stirring and mixing without using water or an organic solvent.

10. The compound according to any one of claims 1 to 9, characterized in that the alkoxytitanium compound has a viscosity of 0.1 to 200 mPa·s at 20°C and a boiling point of 80 to 300°C.

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