JP2021154539A - Process film - Google Patents

Abstract

To provide a process film which has appropriate peeling force while achieving a desired gross value, and can reduce a pinhole generation amount of a sheet-like product under high temperature and high vacuum.SOLUTION: A process film has a base material 20 and a peeling layer 10 formed on at least a part of the surface of the base material 20, in which the peeling layer 10 contains a peeling agent 11 and inorganic particles 12, and the inorganic particles 12 contain at least one kind selected from the group consisting of metal sulfate, metal carbonate, metal carbide and metal nitride. Preferably, silica particles are not contained in the peeling layer 10.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 the process film to the sheet-like product, 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, as the matting agent, a large amount of silica particles having a low price and a low specific density are used as in Patent Document 1. However, due to the hydroxyl groups on the surface of the silica particles, the peeling force increases due to the interaction between the silica particles and the adherend, and there is a risk that the peeling cannot be performed stably. In addition, the hydroxyl groups on the surface of the silica particles adsorb moisture in the air, so that outgas is generated when the process film is processed under high temperature or high vacuum, and pinholes are generated in the resin on the transfer surface of the sheet-like product. In addition, it may have an adverse effect such as contaminating the manufacturing equipment.

Therefore, as one aspect of the present invention, it is possible to achieve a desired gloss value, have an appropriate peeling force, and reduce the amount of pinholes generated in a sheet-like product under high temperature and high vacuum. It is an object of the present invention to provide a process film.

As a result of diligent studies by the present inventor, the above-mentioned problems can be solved by adding at least one selected from the group consisting of metal sulfates, metal carbonates, metal carbides and metal nitrides as inorganic particles to the release layer. We found that we could overcome it, and came to the present invention.

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,
The process film is characterized in that the inorganic particles are at least one selected from the group consisting of metal sulfates, metal carbonates, metal carbides and metal nitrides.

[2] The process film according to [1], wherein the release layer does not contain silica particles.

[3] The process film according to [1] or [2], wherein the inorganic particles contain only a metal sulfate and / or a metal carbonate.

[4] The process film according to any one of [1] to [3], wherein the content of the inorganic particles in the release layer is 30% by mass or more and 80% by mass or less.

[5] The process film according to any one of [1] to [4], wherein the release agent is made of a silicone-modified alkyd resin.

[6] The process film according to any one of [1] to [5], wherein the base material is a polyester film.

According to one aspect of the present invention, it is possible to achieve a desired gloss value, have an appropriate peeling force, and reduce the amount of pinholes generated in a sheet-like product under high temperature and high vacuum. It becomes possible to provide a process film.

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 described later, and if necessary, an additive and an organic solvent are blended.

(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, as the component to be chemically modified, for example, it has 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 are at least one selected from the group consisting of metal sulfates, metal carbonates, metal carbides and metal nitrides. By blending these, it is possible to suppress the generation of outgas while achieving both gloss and peeling power.

Examples of the metal sulfate include sulfates of alkaline earth metals such as calcium sulfate, strontium sulfate and barium sulfate, sulfates of transition metals such as titanium sulfate, lead sulfate and silver sulfate, and basic lead sulfate and the like. Examples include metal sulfate.

Examples of the metal carbonate include calcium carbonate, strontium carbonate, barium carbonate, ferrous carbonate, magnesium carbonate, sodium carbonate, lead carbonate, zinc carbonate and the like.

Examples of the metal carbide include aluminum carbide, silicon carbide and the like.

Examples of the metal nitride include lithium nitride, titanium nitride, aluminum nitride, boron nitride, vanadium nitride, zirconium nitride and the like.

Among these inorganic particles 12 blended in the release layer 10, it is preferable to contain a metal sulfate and / or a metal carbonate from the viewpoint of chemical stability against high temperature, gloss-imparting property and peeling power, and an alkaline earth metal. Sulfate is more preferred, and barium sulfate is even more preferred.

Further, these inorganic particles 12 preferably have an organic group, a reactive functional group, or the like on the surface of the inorganic particles 12 for the purpose of improving dispersibility and imparting reactivity with the release agent 11.

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 lowering the glossiness.

The content of the inorganic particles 12 in the release layer 10 is preferably 30% by mass or more and 80% by mass or less, more preferably 35% by mass or more and 75% by mass or less, and 40% by mass or more and 70% 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 D 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 Particles It is preferable that the release layer 10 does not contain silica particles. By not containing the silica particles, it is possible to suppress the generation of high temperature and high vacuum outgas due to the hydroxyl groups on the surface of the silica particles adsorbing the moisture in the air.

(2-4) 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.

2. 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 includes the release agent 11 and the above. By including the inorganic particles 12, it is possible to achieve a desired gloss as the process film 1, have an appropriate peeling force, and reduce the amount of outgas generated under high temperature and high vacuum. Specifically, the peeling force against the 31B tape measured by the method described in Examples described later is preferably 500 mN / 20 mm or less, more preferably 300 mN / 20 mm or less, and even more preferably 150 mN / 20 mm or less. The lower limit of the peeling force is not particularly limited, but is preferably 10 mN / 20 m or more.

At the same time, the surface of the process film 1 of the present invention has a gloss value of 15% or less at 60 ° and a gloss value of 15% or less at 85 ° with respect to the transfer resin measured by the method described in Examples described later, more preferably. Is a gloss value of 10% or less at 60 ° and a gloss value of 13% or less at 85 °, more preferably a gloss value of 8% or less at 60 ° and a gloss value of 10% or less at 85 °.

3. 3. 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.

4. 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 formulation of the release layer forming composition, particles described below are mixed 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. Was added and dispersed at 2000 rpm for 20 minutes using a disper. As the particles, barium sulfate (trade name: B-2, Sakai Chemical Industry Co., Ltd., average particle diameter 2.0 μm) was added so that the particle mass ratio in the coating film after drying and curing was 40 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 as a curing catalyst, and the mixture was stirred at 1500 rpm for 5 minutes using a disper. 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 3.0 μm was prepared.

[Example 2]
A process film was produced in the same manner as in Example 1 except that the particles were added so that the particle mass ratio in the coating film was 70% by mass.

[Example 3]
The coating liquid is the same as in Example 1 except that the silicone-modified alkyd resin solution is replaced with a silicone-modified acrylic resin solution (trade name: X-62-9089, manufactured by Hitachi Chemical Polymer Co., Ltd.) by 100 parts by mass. To prepare a process film.

[Example 4]
Except that barium sulfate (trade name: BMH-60, manufactured by Sakai Chemical Industry Co., Ltd.) and an average particle diameter of 7.0 μm were added as particles so that the particle mass ratio in the coating film was 40% by mass, the same as in Example 1. A process film was produced in the same manner.

[Comparative Example 1]
Atypical silica particles (trade name: Nipseal SS-50B, manufactured by Tosoh Silica Co., Ltd.) and an average particle size of 2.0 μm were added as particles so that the particle mass ratio in the coating film was 20% by mass. A process film was produced in the same manner as in Example 1.

[Comparative Example 2]
A process film was prepared in the same manner as in Example 1 except that amorphous silica particles (trade name: Nipseal E-220A, manufactured by Tosoh Silica Co., Ltd.) and an average particle diameter of 1.7 μm were changed to 20 parts by mass. bottom.

[Evaluation method]
<Measurement of average particle size of inorganic particles>
The average particle size of the inorganic particle components in the release layer forming compositions of Examples and Comparative Examples was measured using a laser diffraction / scattering type particle size distribution measuring device “Master Sizar 3000” (Marvern Panasonic). The results are shown in Table 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.

<Number of pinholes>
A thermosetting acrylic resin (trade name: UC-3000, manufactured by Toagosei Co., Ltd.) is applied to the surface of the release layer of the process film produced in Examples and Comparative Examples, and heated at 160 ° C. for 30 seconds to form a coating film. Was cured to prepare an acrylic coating film having a thickness of about 3 μm on the process film. This laminate was placed in a vacuum dryer with a vacuum pump (trade name: LCV-234P, manufactured by ESPEC CORPORATION) and left at 180 ° C. for 5 minutes in an environment of ^{1 × 10 -1 Pa.} Then, the acrylic resin film was peeled off from the process film, and the number of pinholes on the surface of the acrylic resin film was visually evaluated. Pinholes ○ those which are 0-5 / ^{m 2,} pinholes △ those which are 6-10 / ^{m 2,} pinholes was × those 11 or more / ^{m 2} could be confirmed. The results are shown in Table 1.

<Glossiness of process film>
The glossiness at angles of 60 ° and 85 ° was measured with respect to the surfaces of the process films obtained in Examples and Comparative Examples using a gloss meter (product name: VG7000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). The results are shown in Table 1.

<Glossiness to 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 was peeled from the process film, and the gloss values of 60 ° and 85 ° on the surface (peeled surface) of the acrylic resin film were measured. The results are shown in Table 1.

The process films of Examples 1 to 5 had an appropriate peeling force and generated less pinholes. Further, it was found that the resin film (sheet-like product) produced by using the process film has a low glossiness and is suitable as a matte film.

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 inorganic particles contain at least one selected from the group consisting of metal sulfates, metal carbonates, metal carbides and metal nitrides. The process film according to claim 1, wherein the release layer does not contain silica particles. The process film according to claim 1 or 2, wherein the inorganic particles contain only a metal sulfate and / or a metal carbonate. The process film according to any one of 1 to 3, wherein the content of the inorganic particles in the release layer is 30% by mass or more and 80% by mass or less. The process film according to any one of claims 1 to 4, wherein the release agent is made of a silicone-modified alkyd resin. The process film according to any one of claims 1 to 5, wherein the base material is a polyester film.

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