JP2021154538A - Process film - Google Patents

Abstract

To provide a process film having appropriate peeling force, while achieving a desired gross value.SOLUTION: A process film 1 comprising; a base material 20 and a peeling layer 10 formed on at least a portion of the surface of the substrate 20, in which the release layer 10 contains a peeling agent 11 and inorganic particles 12, and the inorganic particle has hydrophobicity of the inorganic particles 12 measured by the methanol titration method of 20% or larger. The inorganic particles 12 are preferably surface treated with silicone oil or silane coupling agent.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to process films.

Conventionally, in the manufacturing process of sheet-shaped products such as label materials, electronic devices, prepregs, and synthetic leather, so-called process films are used to protect / fix the sheet-shaped products and impart decorativeness.

In recent years, there has been a demand for sheet-like products that reduce the gloss (glossiness) of the surface and give a matte (matte) tone. A process for reducing the gloss of a sheet-like product As a general structure of a film, a release layer is provided on one side of a base material, particles are added as a matting agent to the release layer forming composition, and the coating film surface is coated. Examples thereof include those having a concavo-convex shape. By transferring the uneven shape portion of this process film to a sheet-like product (adhesive body), a sheet-like product having a matte surface can be obtained.

As a process film used in producing a matte sheet-like product, for example, Patent Document 1 has a base material layer and a particle-containing matte layer on at least one surface of the matte layer. A biaxially oriented polyester film in which the particles are amorphous silica is disclosed.

Japanese Unexamined Patent Publication No. 2016-07522

Generally, inorganic particles such as silica particles and metal particles are used as the matting agent, and a large amount of the inorganic particles are added to the release layer in order to achieve a desired gloss value. .. However, since many hydroxyl groups are present on the surfaces of silica particles and metal particles, the peeling force increases due to the interaction between the hydroxyl groups on the surface of the inorganic particles and the resin sheet-like product, and the peeling becomes stable. There was a risk that it could not be done.

Therefore, one aspect of the present invention is to provide a process film having an appropriate peeling force while achieving a desired gloss value.

As a result of diligent studies by the present inventor, it has been found that the above problems can be overcome by subjecting the surface of the inorganic particles to a hydrophobic treatment and adding the inorganic particles having a surface hydrophobicity satisfying a specific range to the release layer. rice field.

The first aspect of the present invention is
[1] A base material and a release layer formed on at least a part of the surface of the base material are provided.
The release layer contains a release agent and inorganic particles,
It is a process film characterized in that the degree of hydrophobization of the inorganic particles measured by the methanol titration method is 20% or more.

[2] The process film according to [1], wherein the inorganic particles are particles whose surface is hydrophobized with silicone oil.

[3] The process film according to [1], wherein the inorganic particles are particles whose surface is hydrophobized with a silane coupling agent.

[4] The process film according to any one of [1] to [3], wherein the inorganic particles are one or more selected from the group consisting of silica, alumina and titanium oxide. ..

[5] The process film according to [2], wherein the silicone oil is a dimethyl silicone oil.

[6] The process film according to any one of [1] to [5], wherein the glossiness of the release layer is 10% or less at a gloss value of 60 °.

According to one aspect of the present invention, it is possible to provide a process film having an appropriate peeling force while achieving a desired gloss value.

It is sectional drawing which shows the cross section of the process film in one Example.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[Process film]
As shown in FIG. 1, the process film 1 of the present invention includes a base material 20 and a release layer 10 formed on at least a part of the surface of the base material 20, and the release layer 10 is a release agent. 11 and inorganic particles 12 are contained.

1. 1. Each member (1) Base material The base material 20 of the process film 1 can be appropriately selected as long as it can support the release layer 10 described later, and examples thereof include a paper base material and a resin film.

Examples of the paper base material include high-quality paper, medium-quality paper, glassin paper, art paper, coated paper, cast-coated paper, and the like, and a laminate obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials. Paper is also mentioned.

Examples of the resin film include a film made of polyester such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, a film made of polyolefin such as polyethylene, polypropylene, and polymethylpentene, and a film made of plastic such as polycarbonate and polyvinyl acetate. Can be mentioned.

These base materials 20 may be a single layer, or may be two or more layers of the same type or different types.

Among these base materials 20, a polyester film is preferable, a polyethylene terephthalate film is more preferable, and a biaxially stretched polyethylene terephthalate film is further preferable. The polyethylene terephthalate film is less likely to generate dust or the like during processing, use, etc., and can effectively prevent poor coating.

The thickness of the base material 20 is not particularly limited, but is preferably 5 μm or more and 300 μm or less, and more preferably 10 μm or more and 200 μm or less.

(2) Release layer The release layer forming composition for forming the release layer 10 includes a release agent 11 and inorganic particles 12 having a predetermined degree of hydrophobicity, which will be described later, and if necessary, an additive and an organic solvent are blended. do.

(2-1) Release Agent As the release agent 11 contained in the release layer forming composition forming the release layer 10, for example,
(1) A polymer compound having low polarity and exhibiting peelability by itself,
(2) A polymer material that has been chemically modified to give it peelability.
(3) Examples thereof include a composition obtained by adding a peelable low molecular weight or oligomer component to a polymer material to impart peelability.

Examples of the polymer compound having low polarity and exhibiting peelability by itself include polyorganosiloxane; fluoropolymer; polyolefin such as polyethylene, polypropylene and polymethylpentene; and diene-based polymer such as polybutadiene and polyisoprene.

In a polymer material that has been chemically modified to provide peelability, examples of the chemically modified polymer component include polyvinyl alcohol, partially saponified polyvinyl acetate, hydroxyl group-containing acrylic ester copolymer, urethane resin, and alkyd resin. , Amino resin, epoxy resin, phenol resin and the like. These polymer components often do not exhibit peelability unless they are chemically modified.

Further, in the polymer material to which the peelability is imparted by chemical modification, examples of the component to be chemically modified include a polyorganosiloxane or an organosiloxane oligomer having a functional group; a fluorocarbon compound having a functional group; and a functional group. Long chain alkyl compounds can be mentioned. Examples of the long-chain alkyl compound include compounds having an alkyl group having 12 or more carbon atoms, such as a lauryl group, a palmityl group, and a stearyl group.

Examples of the functional group of the chemically modified compound include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a (meth) acryloyl group, a thiol group, and an alkoxysilyl group.

Polymer materials that have been chemically modified to give them releasability are usually referred to as silicone-modified resins, fluoro-modified resins, and long-chain alkyl-modified resins.

Examples of the polymer material used in the composition obtained by adding a releasable low molecular weight or oligomer component to the polymer material to impart releasability include polyvinyl alcohol, partially saponified polyvinyl acetate, and acrylic acid ester copolymer. Examples thereof include urethane resin, polyester resin, polyamide resin, alkyd resin, amino resin, epoxy resin, and phenol resin.

Examples of the peelable low molecular weight or oligomer component added to these polymer materials include wax (hydrocarbon compound); polyorganosiloxane or organosiloxane oligomer; fluorocarbon; long-chain alkyl compound, and further these polys. Examples include ether adducts and polyester adducts. Among these, polymers that have been chemically modified to give them releasability from the viewpoint that their releasability and heat resistance can be easily improved and their affinity with fillers and other additives can be improved. The material is preferable as a peelable main agent, and an alkyd resin chemically modified with polyorganosiloxane, a so-called silicone-modified alkyd resin, is more preferable. The above-mentioned peelable main agent may be used alone or in combination of two or more.

(2-2) Inorganic Particles The inorganic particles 12 added to the release layer 10 have a degree of hydrophobization of 20% or more by the methanol titration method. The degree of hydrophobicity of the inorganic particles 12 is more preferably 25% or more, further preferably 30% or more. When the degree of hydrophobicity of the inorganic particles 12 is in the range of 20% or more, the interaction between the inorganic particles 12 and the resin sheet-like product can be weakened, and the peeling force can be controlled. The upper limit of the degree of hydrophobicity of the inorganic particles 12 is not particularly limited, but is 100% or less, more preferably 90% or less, still more preferably 80% or less. The degree of hydrophobization by the methanol titration method according to the present invention refers to those measured under the following conditions.

0.2 g of a sample (inorganic particles) is added to a predetermined amount (50 mL) of ion-exchanged water, and methanol is added dropwise with stirring. The degree of hydrophobization can be obtained by the following equation when the amount of methanol added to the end point is G (mL), starting from the time when the total amount of the sample is no longer recognized on the liquid surface.
Degree of hydrophobization = {G (mL)} / {G (mL) + amount of ion-exchanged water (50 mL)} x 100

Examples of the inorganic particles 12 include silica, alumina, titanium oxide, zinc oxide, calcium carbonate, magnesium hydroxide, aluminum hydroxide, kaolin, talc, clay and the like. Among these, one or more selected from amorphous silica and amorphous alumina is preferable from the viewpoint of heat resistance, and it is more preferable to use amorphous silica from the economical viewpoint.

The degree of hydrophobization of the inorganic particles 12 can be controlled by appropriately selecting the formation conditions of the inorganic particles 12, the presence or absence of the hydrophobization treatment, and the hydrophobization treatment conditions when the hydrophobization treatment is carried out.

As a method for hydrophobizing the inorganic particles 12, a known method can be used, and for example, a dry method or a wet method can be used.

In the case of the dry method, the inorganic particles 12 are stirred with a mixer having a large shearing force or the like, and a hydrophobic treatment agent dissolved directly or in an organic solvent or water is dropped and sprayed together with dry air or nitrogen gas to cause the inorganic particles. The surface of 12 can be treated uniformly. The hydrophobizing agent is preferably added dropwise or sprayed at a temperature of 50 ° C. or higher. After dropping or spraying the hydrophobizing agent, baking may be further performed at 100 ° C. or higher. Further, in the dry method, the surface-adsorbed water can be removed by heating and drying the inorganic particles 12 before hydrophobizing the surface with the hydrophobizing agent. By removing the surface-adsorbed water in the hydrophobizing treatment of the inorganic particles 12, the hydrophobizing agent can be uniformly adsorbed on the surface of the inorganic particles 12. The inorganic particles 12 can also be heat-dried while stirring with a mixer or the like having a large shearing force.

In the case of the wet method, the inorganic particles 12 are dispersed in a solvent by stirring, ultrasonic waves, a sand mill, an attritor, a ball mill, or the like, a hydrophobizing agent solution is added, stirred or dispersed, and then the solvent is removed to remove the inorganic particles. The surface of the particles 12 can be uniformly treated. In the wet method, the surface adsorbed water can be removed before the surface of the inorganic particles 12 is hydrophobized with a hydrophobizing agent. This surface adsorption water removal method is carried out by a method of removing by heating and drying in a solvent used for surface treatment, a method of removing by azeotropically boiling with a solvent, and the like, in addition to the removal by heating and drying as in the dry method. NS. After removing the solvent, baking can be performed at 100 ° C. or higher.

Further, during the preparation of the release layer forming composition described later, the inorganic particles 12 and the hydrophobizing treatment agent may be added and stirred or dispersed to perform surface treatment.

The proportion of the hydrophobizing agent used is preferably 0.05 parts by mass or more and 80 parts by mass or less, and 0.1 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the inorganic particles 12. More preferred. If it is less than 0.05 parts by mass, the surface treatment becomes insufficient, and if it exceeds 80 parts by mass, the post-treatment becomes complicated.

As the hydrophobizing agent, a known one that is usually used for the surface treatment of the inorganic particles 12 can be used without particular limitation, and may be appropriately selected depending on the required performance of the inorganic particles 12 and the like. For example, silicone oil, alkoxysilane, silane coupling agent, titanium coupling agent, halogen compound, siloxane, silazane, higher fatty acid and the like can be mentioned. The above-mentioned hydrophobizing agent may be used alone or in combination of two or more.

Examples of the silicone oil include straight silicone oils such as dimethyl silicone oil, methylhydrogen silicone oil, and methylphenyl silicone oil; alkyl-modified silicone oil, chloroalkyl-modified silicone oil, chlorophenyl-modified silicone oil, fatty acid-modified silicone oil, and polyether. Examples thereof include modified silicone oil, alkoxy-modified silicone oil, carbinol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, fluorine-modified silicone oil, methacryl-modified silicone oil, and mercapto-modified silicone oil.

Examples of the alkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, and phenyltriethoxysilane.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxytrimethoxysilane, and 3-glycidoxypropyltri. Methoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2) -Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N, N-dimethyl-3-aminopropyltrimethoxysilane, N, N-diethyl-3-aminopropyltri Examples thereof include methoxysilane and 4-styryltrimethoxysilane.

Examples of the titanium coupling agent include isopropyltri (N-aminoethylaminoethyl) titanate, isopropyltriisostearoyl titanate, diisopropylbis (dioctylphosphate) titanate, tetraisopropylbis (dioctylphosphate) titanate, and tetraoctylbis (ditri). Decylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate) ethylene titanate, bis (dioctylpyrophosphate) oxyacetate titanate, etc. Be done.

Examples of the halogen compound include magnesium fluoride, aluminum fluoride, strontium fluoride, barium fluoride, calcium fluoride, ammonium fluoride, magnesium chloride, aluminum chloride, strontium chloride, barium chloride, calcium chloride, ammonium chloride, and odor. Magnesium bromide, aluminum bromide, strontium bromide, barium bromide, calcium bromide, ammonium bromide, magnesium iodide, aluminum iodide, strontium iodide, barium iodide, calcium iodide, ammonium iodide, hydrogen borofluoride Acids, acidic ammonium fluoride, hydrocarbic acid, ammonium fluoride, zinc borofluoride and the like can be mentioned.

Examples of the siloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane and the like.

Examples of the silazane include hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, hexabutyldisilazane, hexapentyldisilazane, hexahexyldisilazane, hexacyclohexyldisilazane, hexaphenyldisilazane, and divinyltetramethyl. Examples thereof include disilazane and dimethyltetravinyl disilazane.

Examples of higher fatty acids include stearic acid, palmitic acid, isoparmitic acid, oleic acid and the like.

Among these, a silane coupling agent or a silicone oil is preferable from the viewpoint of the efficiency of the hydrophobizing treatment. As the silane coupling agent, 3-glycidoxypropylmethyldiethoxysilane and 3-methacryloxypropylmethyldimethoxysilane are preferable, and as the silicone oil, dimethylsilicone oil is preferable.

The shape of the inorganic particles 12 may be spherical, hollow, porous, rod-shaped (referring to a shape having an aspect ratio of more than 1 and 10 or less), plate-like, fibrous, or indefinite shape, and may be any shape. be able to. Among these, an indefinite shape is preferable from the viewpoint of reducing the glossiness of the process film 1 and the sheet-like product obtained by using the process film 1.

The content of the inorganic particles 12 in the release layer 10 is preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 50% by mass or less, and 20% by mass or more and 40% by mass or less. It is more preferable to have. Within this range, an appropriate peeling force can be obtained.

The average particle size of the inorganic particles 12 is preferably 0.5 μm or more and 10.0 μm or less, more preferably 1.5 μm or more and 8.0 μm or less, and preferably 2.0 μm or more and 7.0 μm or less. More preferred. If the average particle size is smaller than 0.5 μm, the inorganic particles 12 are less likely to be exposed from the release layer 10, and the glossiness may be enhanced. Further, when the average particle size is larger than 10.0 μm, the inorganic particles 12 may be exposed too much from the release layer 10 and the matte feeling may become too strong. The average particle size can be measured by a laser diffraction type particle size distribution meter for the release layer forming composition containing the inorganic particles 12 alone or the inorganic particles 12 as a measurement target.

(2-3) Other Components As the curing agent, cross-linking agent and reaction initiator used in the release layer forming composition, a compound having a functional group capable of chemically bonding with the functional group of the release agent 11 is selected. The curing agent, cross-linking agent, and reaction initiator react with the release agent 11 to form a three-dimensional network structure, thereby improving the strength and heat resistance of the film of the release layer 10. The curing agent, cross-linking agent and reaction initiator used in the release layer forming composition are not particularly limited as long as they can react with the functional group of the release agent 11, and for example, a polyvalent hydrosilyl group-containing organosiloxane compound. , Melamine compound, polyvalent isocyanate compound, polyvalent epoxy compound, polyvalent aldehyde compound, polyvalent amine compound, polyvalent oxazoline compound, metal complex and the like.

The catalyst used in the release layer forming composition is a compound that accelerates the curing reaction (crosslinking reaction) of the release layer forming composition so as to proceed at a low temperature or in a short time, and a compound corresponding to the chemical reaction is selected. .. As the catalyst used for the addition reaction with the polyvalent hydrosilyl group-containing organosiloxane compound, for example, a platinum catalyst is used. Further, as a catalyst used for a reaction involving dehydration and dealcoholization with a melamine compound, for example, an acid catalyst such as p-toluenesulfonic acid is used.

In the release layer forming composition, the blending ratio of the curing agent, the cross-linking agent, and the reaction initiator to the release agent 11 may be appropriately selected so as to be suitable for various physical characteristics of the required process film 1. For example, release. With respect to 100 parts by mass of the non-volatile component of the agent 11, 0.1 parts by mass or more and 400 parts by mass or less are preferable, and 10 parts by mass or more and 200 parts by mass or less are more preferable. Similarly, the blending ratio of the catalyst may be appropriately selected so as to be suitable for the required reaction rate of the release layer forming composition and the required physical characteristics of the process film 1. For example, the release agent 11 is non-volatile. It is preferably 0.01 part by mass or more and 10 parts by mass or less, and more preferably 0.5 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the component.

The release layer forming composition for forming the release layer 10 according to the present embodiment contains various additives such as a storage elastic modulus adjusting agent, a colorant such as a dye or a pigment, and a flame retardant in addition to the above components. You may.

The release layer forming composition is preferably used in the form of a solution containing an organic solvent. The organic solvent should be appropriately selected from known organic solvents that have good solubility and volatility in the release layer 10 and are chemically inactive for each component of the release layer forming composition. Can be done. Examples of such an organic solvent include toluene, xylene, hexane, heptane, methanol, ethanol, isopropanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, tetrahydrofuran and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

3. 3. Physical Properties of Process Film The process film 1 of the present invention includes a base material 20 and a release layer 10 formed on at least a part of the surface of the base material 20, and the release layer 10 has a release agent 11 and a predetermined range. By including the inorganic particles 12 having the inner hydrophobicity, it is possible to have an appropriate peeling force while achieving a desired gloss as the process film 1. Specifically, the peeling force with respect to the 31B tape measured by the method described in Examples described later is preferably 6000 mN / 20 mm or less, more preferably 4000 mN / 20 mm or less, and further preferably 3500 mN / 20 mm or less. The lower limit of the peeling force is not particularly limited, but is preferably 100 mN / 20 mm or more.

Further, the peeling force against the transfer resin measured by the method described in Examples described later is preferably 10,000 mN / 50 mm or less, more preferably 9000 mN / 50 mm or less, and further preferably 8000 mN / 50 mm or less. The lower limit of the peeling force is not particularly limited, but is preferably 100 mN / 50 mm or more.

The glossiness of the surface of the release layer 10 of the process film 1 of the present invention is preferably a 60 ° gloss value of 10% or less, more preferably a 60 ° gloss value of 8% or less, as measured by the method described in Examples described later. A 60 ° gloss value of 6% or less is more preferable.

Further, the glossiness of the surface of the transfer resin produced by the process film 1 of the present invention is preferably a 60 ° gloss value of 10% or less, and a 60 ° gloss value of 7% or less, which is measured by the method described in Examples described later. Is more preferable, and a 60 ° gloss value of 5% or less is further preferable.

4. Method for Producing Process Film The method for producing the process film 1 according to the present embodiment includes a first step of mixing a release agent 11 and an inorganic particle 12 to prepare a release layer forming composition, and a release layer forming composition. It is preferable to include a second step of applying the substance to at least a part of the surface of the base material 20 to form a coating film, and a third step of curing the coating film to form a release layer 10.

The method for adjusting the release layer forming composition in the first step is not particularly limited, and for example, it can be prepared as a dispersion or a solution of the release layer forming composition. In the present invention, it is preferable to prepare a solution containing an organic solvent.

The non-volatile content concentration of the solution of the release layer forming composition is preferably 5.0% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less, and 20% by mass from the viewpoint of coating suitability and dryness. % Or more and 40% by mass or less are more preferable.

Examples of the coating method in the second step include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a roll knife coating method, a blade coating method, a die coating method, and a gravure coating method. ..

As a method of curing the coating film in the third step, it may be cured by heating together with drying, and when the components in the coating film have a functional group that reacts with active energy rays, it is cured by irradiation with active energy rays. It may be cured by using heating and irradiation with active energy rays in combination. Examples of the active energy ray include ultraviolet rays and electron beams.

The heating temperature is preferably 80 ° C. or higher and 250 ° C. or lower, and more preferably 100 ° C. or higher and 230 ° C. or lower. The heating time is preferably 15 seconds or more and 5 minutes or less, and more preferably 20 seconds or more and 3 minutes or less.

In the process film 1, the film thickness of the release layer 10 after curing is not particularly limited, but is preferably 0.5 μm or more and 12 μm or less, and more preferably 1.0 μm or more and 8 μm or less.

5. Use of Process Film The process film 1 of the present invention can be used in the manufacturing process of sheet-like products such as label materials, electronic devices, prepregs, and synthetic leather.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereto.

[Example 1]
As a release agent, the inorganic particles described below are added to a mixed solution of 100 parts by mass of a silicone-modified alkyd resin solution (trade name: TA31-209E, manufactured by Hitachi Chemical Polymer Co., Ltd.), 216 parts by mass of toluene, and 144 parts by mass of methyl ethyl ketone to disperse. Was dispersed at 2000 rpm for 20 minutes. As inorganic particles, amorphous silica particles with an average particle diameter of 3.0 μm and a surface modified with polydimethylsiloxane with dimethylsilicone oil and having a degree of hydrophobicity of 60% (trade name: Nipseal SS-50A, manufactured by Tosoh Silica Co., Ltd.) Was added so that the mass ratio of the inorganic particles in the coating film (release layer) after drying was 23.8% by mass. 2.5 parts by mass of a p-toluenesulfonic acid methanol solution (solid content concentration 50% by mass) was added to the mixed solution after dispersion as a curing catalyst, and the mixture was stirred at 1500 rpm for 5 minutes using a disper to form a release layer composition. A solution was obtained. The solution of this release layer forming composition is applied to one side of a polyethylene terephthalate film (trade name: Diafoil T100, manufactured by Mitsubishi Chemical Corporation) having a thickness of 50 μm, dried and cured at 150 ° C. for 1 minute, and after curing. A process film having a release layer having a thickness of 1.5 μm was prepared.

[Example 2]
As inorganic particles, amorphous silica particles with an average particle diameter of 2.0 μm and a surface modified with polydimethylsiloxane with dimethylsilicone oil and having a degree of hydrophobicity of 60% (trade name: Nipseal SS-50B, manufactured by Tosoh Silica Co., Ltd.) Was added so that the mass ratio of the inorganic particles in the coating film (release layer) after drying was 23.8% by mass, and a process film was prepared in the same manner as in Example 1.

[Example 3]
As inorganic particles, amorphous silica particles with an average particle diameter of 1.3 μm and a surface modified with polydimethylsiloxane with dimethylsilicone oil and having a degree of hydrophobicity of 60% (trade name: Nipseal SS-50G, manufactured by Tosoh Silica Co., Ltd.) Was added so that the mass ratio of the inorganic particles in the coating film (release layer) after drying was 23.8% by mass, and a process film was prepared in the same manner as in Example 1.

[Example 4]
As an inorganic particle, the surface is unmodified in a mixed solution of 100 parts by mass of a silicone-modified alkyd resin solution (trade name: TA31-209E, manufactured by Hitachi Chemical Polymer Co., Ltd.), 216 parts by mass of toluene, and 144 parts by mass of methyl ethyl ketone as a release agent. Atypical silica particles (trade name: Nipseal E-200A, manufactured by Toso Silane Co., Ltd.) were added so that the mass ratio of the inorganic particles in the coating film (release layer) after drying was 23.8% by mass. Further, 0.4 parts by mass of 3-glycidoxypropylmethyldiethoxysilane (trade name: KBM-402, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added as a silane coupling agent, and the mixture was dispersed at 2000 rpm for 20 minutes using a disper. .. To the mixed solution after dispersion, 2.5 parts by mass of a p-toluenesulfonic acid methanol solution (solid content concentration 50% by mass) was added as a curing catalyst, and the mixture was further stirred at 1500 rpm for 5 minutes using a disper to form a release layer composition. Solution was obtained. The solution of this release layer forming composition is applied to one side of a polyethylene terephthalate film (trade name: Diafoil T100, manufactured by Mitsubishi Chemical Corporation) having a thickness of 50 μm, dried and cured at 150 ° C. for 1 minute, and after curing. A process film having a release layer having a thickness of 1.5 μm was prepared. The degree of hydrophobization of the inorganic particles was 30%.

[Example 5]
A process film was produced in the same manner as in Example 4 except that 3-methacryloxypropylmethyldimethoxysilane (trade name: KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent. The degree of hydrophobization of the inorganic particles was 35%.

[Comparative Example 1]
As inorganic particles, a coating film (trade name: Nipseal E-200A, manufactured by Tosoh Silica Co., Ltd.) after drying atypical silica particles (trade name: Nipseal E-200A, manufactured by Tosoh Silica Co., Ltd.) having an average particle diameter of 3.0 μm, an unmodified surface and a degree of hydrophobicity of 0%. A process film was produced in the same manner as in Example 1 except that the particles were added so that the mass ratio of the inorganic particles in the release layer) was 23.8% by mass.

[Comparative Example 2]
As inorganic particles, a coating film (trade name: Nipseal E-220A, manufactured by Tosoh Silica Co., Ltd.) after drying atypical silica particles (trade name: Nipseal E-220A, manufactured by Tosoh Silica Co., Ltd.) having an average particle diameter of 1.7 μm, an unmodified surface and a degree of hydrophobicity of 0%. A process film was produced in the same manner as in Example 1 except that the particles were added so that the mass ratio of the inorganic particles in the release layer) was 23.8% by mass.

[Evaluation method]
<Measurement of average particle size of inorganic particles>
The solution of the release layer forming composition was used as a measurement target, and the average particle size of the inorganic particles was measured using a laser diffraction / scattering type particle size distribution measuring device “Master Sizar 3000” (Malvern Panasonic). The results are shown in Table 1.

<Measurement of hydrophobicity (methanol titration method)>
The degree of hydrophobization of the inorganic particles used in Examples and Comparative Examples was measured as follows. For the inorganic particles of Examples 4 and 5, the degree of hydrophobicity of the inorganic particles separated from the solution of the release layer forming composition by using a centrifuge was measured. 50 ml of ion-exchanged water is placed in a 200 ml beaker, and 0.2 g of a sample (inorganic particles) is added. Add methanol with a dropper (burette) while stirring with a stirrer. The degree of hydrophobization is calculated by the following formula (1) from the amount of methanol required from the time when the sample is no longer recognized on the liquid surface as the end point. G in the formula represents the amount of methanol used (ml).
Degree of hydrophobization (%) = (G / G + 50) × 100 ・ ・ ・ (1)

<Peeling force against 31B tape>
A polyester tape with an acrylic adhesive (trade name: No. 31B tape, manufactured by Nitto Denko Co., Ltd.) was attached to the surface of the process films obtained in Examples and Comparative Examples, and in a constant temperature room at 23 ° C. and 50% relative humidity. After leaving it for 30 minutes, it was cut into a width of 20 mm and a length of 150 mm. Using a tensile tester (device name: Tencilon, manufactured by A & D Co., Ltd.), the 31B tape was pulled in the 180 ° direction at a speed of 300 mm / min, and the peeling force at the time of peeling was measured. The results are shown in Table 1.

<Peeling force against transfer resin>
A thermosetting acrylic resin (product name: UC-3000, manufactured by Toagosei Co., Ltd.) is applied to the surface of the process films obtained in Examples and Comparative Examples to obtain a laminate of the coating film and the process film. rice field. The coating film was cured by heating at 160 ° C. for 30 seconds to prepare an acrylic coating film having a thickness of about 3.0 μm on the process film. The acrylic coating film is cut into a width of 50 mm and a length of 150 mm, and is 300 mm in a constant temperature room at 23 ° C. and a relative humidity of 50% using a tensile tester (device name: Tencilon, manufactured by A & D Co., Ltd.). The peeling force at the time of peeling was measured by pulling in the 180 ° direction at a speed of / min. The results are shown in Table 1.

<Glossiness of process film>
In accordance with JIS Z 8741, the glossiness (60 ° gloss value) of the process film surface obtained in Examples and Comparative Examples is measured using a gloss meter (product name: VG7000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). bottom. The results are shown in Table 1.

<Glossiness of transfer resin>
A thermosetting acrylic resin (trade name: UC-3000, manufactured by Toagosei Co., Ltd.) is applied to the surface of the process films obtained in Examples and Comparative Examples to obtain a laminate of the coating film and the process film. rice field. The coating film was cured by heating at 160 ° C. for 30 seconds to prepare an acrylic coating film having a thickness of 3 μm on the process film. The obtained acrylic resin film is peeled off from the process film, and the glossiness (60 ° gloss) of the surface of the acrylic resin film is (60 ° gloss) using a gloss meter (product name: VG7000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS Z 8741. Value) was measured. The results are shown in Table 1.

The process films of Examples 1 to 5 had an appropriate peeling force and a low glossiness, and a transfer resin (sheet-like product) having a low glossiness could be obtained by using the process films.

Although each embodiment has been described in detail above, the present invention is not limited to a specific embodiment, and various modifications and changes can be made within the scope of the claims. It is also possible to combine all or a plurality of the components of the above-described embodiment.

1 Process film 10 Release layer 11 Release agent 12 Inorganic particles 20 Base material

Claims (6)

A base material and a release layer formed on at least a part of the surface of the base material are provided.
The release layer contains a release agent and inorganic particles,
A process film characterized in that the degree of hydrophobization of the inorganic particles measured by the methanol titration method is 20% or more. The process film according to claim 1, wherein the inorganic particles are particles whose surface is hydrophobized with silicone oil. The process film according to claim 1, wherein the inorganic particles are particles whose surface is hydrophobized with a silane coupling agent. The process film according to any one of claims 1 to 3, wherein the inorganic particles are one or more selected from the group consisting of silica, alumina and titanium oxide. The process film according to claim 2, wherein the silicone oil is a dimethyl silicone oil. The process film according to any one of claims 1 to 5, wherein the peeling layer has a glossiness of 10% or less in a 60 ° gloss value.

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