JPH05269935A - Peeling sheet for processing mat surface - Google Patents

Abstract

PURPOSE:To form a frosted face and manufacture efficiently by coating one face of a substrate with a peeling layer comprising a silicone compound curable by electron radiation of viscosity of 10-200cps and one or more kinds of pigments selected out of organic and inorganic pigments having the average grain diameter of 3mum or smaller as main components. CONSTITUTION:A peeling layer comprising a silicone compound curable by electron radiation of 10-200cps of viscosity, the average composition of which is represented by the formula I (R<1> is hydrogen atom or straight chain, branched or cyclic 1-6C alkyl, allyl, alkoxy or hydroxyl, and at least 80mol% or more is methyl. R<2> is -CnH2n-OCOC(R<3>)=CH2, and n is 0-6. R<3> reprents hydrogen atom or methyl, and a and b represent the composition ratio and b=0.016-0.45 and 1.8<a+b<2.3.) and one or more kinds of pigments selected out of organic and inorganic pigments having the average grain diameter of 3mum or smaller as main components is formed at least one face of a substrate. The peeling layer is made to adhere closely to a mat surface roll and then cured through irradiation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a release sheet for a process, and more specifically, it is a release sheet having a release layer provided on a paper or film support, and is particularly useful in the production process of synthetic leather, marking film and the like. The present invention relates to a matte surface release sheet having a matte surface used.

[0002]

2. Description of the Related Art A release sheet for process is a synthetic fiber, prepreg, which has a release layer made of polypropylene resin, silicone resin, aminoalkyd resin on a support such as long-fiber high-quality paper or coated paper. It is used as a carrier for casting synthetic resins such as urethane paste and vinyl sol in the manufacturing process of flooring materials, marking films, and various molded products.

As a method for forming the release layer of the release sheet for these processes, after coating a solution or emulsion of a reactive silicone resin or aminoalkyd resin,
A method of forming a cured coating by heating at 120 ° C to 200 ° C in a heat oven is common.

In a release sheet for processes using paper such as long-fiber high-quality paper or coated paper as a support, it is needless to say that the paper support is required to have heat resistance when subjected to such high temperature heat treatment, Wrinkles, curls, due to water evaporation inside the paper support
It had a drawback that pinholes were likely to occur.

In recent years, as a technique for producing such a release sheet, a solventless silicone resin, in particular, a silicone resin having a functional group which can be polymerized by irradiation of ultraviolet rays and electron beams is used, and it is coated on a support and is exposed to ultraviolet rays or electrons. A low-temperature curing type manufacturing technique for performing line hardening has been developed (JP-A-60-190427 and JP-A-60-25).
8280).

According to these methods, curls, wrinkles, and the like resulting from the high temperature treatment in the conventional production of release sheets for processes,
Although it is possible to prevent the occurrence of pinholes, etc., it has better releasability than solvent coated aminoalkyd resin, but it has a serious manufacturing problem that a matte surface cannot be obtained. It was That is, in the case of a resin containing a pigment using a solvent, the pigment protrudes to the surface with the evaporation of the solvent after coating, and a good matte surface is obtained, but in an ultraviolet ray or electron beam curable silicone resin where evaporation cannot be expected. Since the pigment surface is cured while the silicone resin layer is covered, the surface must always be a wet release glossy sheet and a release sheet for processes having a relatively smooth surface property. Naturally, such a glossy surface does not become a matte surface when a surface is transferred by coating a resin on a release sheet for process, and it has a glossy or glossy feeling and is relatively smooth. Only a good transfer surface can be obtained. Even when a resin composition in which a pigment is mixed with an ultraviolet ray or electron beam curable silicone resin is used, if the coating is sufficiently thin, the surface of the pigment is projected and a matte feeling can be obtained. The effect of the silicone resin as a binder becomes small, and the pigment and silicone resin layer fall off from the support when the matte surface created is lightly rubbed, and it cannot withstand repeated use, and can be used as a release sheet for matte surface process. There was a serious problem that I could not.

[0007]

SUMMARY OF THE INVENTION Therefore, the problem to be solved by the present invention is to provide a release layer having excellent matting property and matting agent retention property in the production of various molded articles such as synthetic leather and marking films. The purpose is to supply a release sheet for matte surface process, which is excellent in the number of times of repeated use.

[0008]

As a result of earnest research on means for solving the above-mentioned problems, the present inventors have invented a release sheet for mat surface process which solves the above-mentioned problems. That is, the release sheet for mat surface process of the present invention,
Average composition formula 2 (general formula 1) on at least one side of the support
A release layer mainly composed of an electron beam curable silicone compound having a viscosity of 10 to 200 cps and at least one pigment selected from organic pigments and inorganic pigments having an average particle diameter of 3 μm or less. Is an invention of a release sheet for matte surface process, which is formed by coating.

[0009]

[Chemical 2]

The present invention will be described in detail below.

The present invention relates to a release sheet for a process, and more particularly to a release sheet for a matte surface process used in the production of various molded products such as synthetic leather and marking films.

The release sheet for matte surface process according to the present invention comprises an electron beam curable silicone compound having a certain proportion or more of acryloyl groups introduced at the molecular ends and side chains, and an inorganic pigment having an average particle size of 3 μm or less, By providing a release layer formed by coating a release layer containing at least one pigment selected from among organic pigments as a main component, the acryloyl group has an aggregating effect at the time of curing, resulting in an excellent characteristic of silicone resin. The glossiness, which was a defect of conventional electron beam curable silicone resins, was reduced without impairing the peelability, and the coating strength and pigment retention were significantly improved due to the effect of the acryloyl group introduced into the silicone skeleton. It is a thing.

The electron beam-curable silicone compound represented by the general formula 1 of the present invention has an adhesiveness between a support and a release layer,
It can be used alone or in combination with an electron beam curable binder having no silicone skeleton in consideration of migration and peel strength control of the electron beam curable silicone compound.

The pigment used in the present invention as a matting agent together with the silicone compound includes calcium carbonate, magnesium carbonate, silicon dioxide, titanium dioxide, zinc oxide,
Aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, zinc sulfate,
Kaolin, talc, clay, calcined kaolin, calcined clay, lithopone, satin white, inorganic pigments such as silica / alumina, polyethylene, polypropylene, Teflon, polystyrene, starch, urea-formalin resin,
Powders such as polyacrylic resins, melamine resins and silicone resins are used as organic pigments. Further, it is also possible to use a surface-treated inorganic pigment, especially from the dispersibility with an electron beam curable silicone compound,
An inorganic pigment that has been subjected to a hydrophobic treatment is preferably used. A suitable average particle size of the pigment is 0.5 to 3 μm. If the average particle size is smaller than this range, the matte effect is small and the desired matte surface cannot be obtained. If the average particle size is larger than this range, it is uniform. No matte feeling is obtained, and it becomes brittle against friction, and scratch resistance is deteriorated.

The electron beam curable binder which can be mixed with the electron beam curable silicone compound represented by the general formula 1 of the present invention has an unsaturated bond which can be polymerized by an electron beam which is usually used in this field. Any compound can be used. That is, a compound having one or more carbon-carbon unsaturated bonds, an acryloyl group,
A compound containing a methacryloyl group, an acrylamide group, an allyl group, a vinyl ether group, a vinyl thioether group, and the like, for example, an alkyl acrylate ester, an alkyl methacrylate ester, acrylonitrile, methacrylonitrile, acrylamide, vinyl acetate, vinyl propionate, vinyl. Examples include pyrrolidone. There may be two or more unsaturated bonds in the molecule. In particular, unsaturated esters of polyols such as ethylene diacrylate, diethylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and the like can be mentioned. A compound having one or more epoxy rings, such as glycidyl acrylate, is also preferable. Furthermore, these compounds may be high molecular weight compounds. A compound having an acrylate group at the terminal or side chain of the polymer chain is particularly preferable, and examples thereof include a prepolymer having a polyester skeleton, a polyurethane skeleton, an epoxy resin skeleton, a polyether skeleton, and a polycarbonate skeleton. These monomers and prepolymers may be used alone or as a mixture, but the adhesion between the support and the release layer is improved, the rub-off is reduced, and electron beam curing is possible when an adhesive layer is provided on the release layer. In consideration of reduction of migration of the silicone compound to the adhesive layer, it is more preferable to use a monomer or prepolymer having two or more functional groups capable of polymerization by electron beam, mixed with the electron beam-curable silicone compound.

In order to make the mixing of the electron beam curable silicone compound and the electron beam curable binder uniform,
A surfactant or the like may be mixed.

When preparing a composition for forming a release layer containing an electron beam-curable silicone compound as a main component, the electron beam-curable silicone compound and each of the above components are kneaded at the same time or individually. Put it in the machine and do it. Various kneaders are used for kneading and dispersing the composition. For example, a two-roll, a three-roll, a ball mill, a sand grinder, a disper, a high-speed impeller disperser, a high-speed mixer homogenizer and the like.

As the support used in the present invention, glassine paper, high-quality paper, paperboard, coated paper provided with a coating layer,
Various types of paper such as cast paper, polyethylene, polypropylene, polyethylene terephthalate, synthetic resins such as polyamide, or laminated paper, non-woven fabric, or metal foil and paper laminated with one side or both sides of these synthetic resins on paper,
It refers to a product laminated with a synthetic resin film, etc., and any material that can be generally used as a support for a release sheet for processes can be used in the present invention. In particular, a coated paper obtained by subjecting the surface of natural pulp paper to aqueous coating and calendering for the purpose of preventing excessive entrapment of a release layer-forming composition containing an electron beam-curable silicone compound as a main component into the support. Is effectively used. The aqueous coating referred to here is a coating liquid obtained by dissolving or dispersing at least one kind of a water-soluble polymer and a water-dispersible polymer and a pigment in water, and then drying it to form a layer. It means that.

Examples of the water-soluble polymer used in the aqueous coating include the following. Examples of natural polymers and semisynthetic polymers include modified starch compounds such as starch, oxidized starch, etherified starch, dialdehyde starch, esterified starch, alginic acid compounds such as sodium alginate and propylene glycol alginate, casein, gelatin, Pullulan, dextran, chitin, chitosan, gum arabic,
Funori, natural gum, dextrin, methyl cellulose,
Examples thereof include modified cellulose compounds such as ethyl cellulose, hydroxy cellulose and carboxymethyl cellulose. As the synthetic polymer, completely saponified or partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, esterification products of polyvinyl alcohol and polyvalent carboxylic acid, carboxy modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, olefin modified Modified polyvinyl alcohol compounds such as polyvinyl alcohol, nitrile modified polyvinyl alcohol, amide modified polyvinyl alcohol, pyrrolidone modified polyvinyl alcohol, polyethylene glycol, polyacrylic acid amide, polyacrylic acid, ammonium polyacrylate, sodium polyacrylate, etc. Polyacrylic acid compound, polyvinylpyrrolidone, polyethyleneimine, polyvinyl ether, polymaleic acid copolymer, water-soluble alkyd resin And the like. Further, examples of the water-dispersible polymer include the following. Examples thereof include various latexes in which a synthetic polymer such as a styrene-maleic anhydride copolymer, a styrene-butadiene copolymer, a butadiene-methacrylate copolymer is dispersed in water. As the water-soluble polymer and the water-dispersible polymer, the above polymers may be used alone or as a mixture, and used as an aqueous solution.

Typical examples of pigments used for aqueous coating include calcium carbonate, silicon dioxide, titanium dioxide, zinc oxide, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, zinc sulfate and kaolin. , Inorganic pigments such as talc, clay, calcined kaolin and calcined clay, and organic pigments such as polyethylene powder, polystyrene powder and urea-formalin resin powder.

If necessary, various auxiliary agents such as a surfactant and a defoaming agent may be mixed in the coating solution.

The basis weight of the support varies depending on the type of support, for example in the case of paper, 40~250g / m ^2, more preferably from 100 to 200 g / m ^2. Before the release layer is provided on the support, the support surface may be subjected to surface treatment such as corona discharge in order to further improve the adhesion of the release layer.

As a method of providing a release layer containing an electron beam-curable silicone compound as a main component on a support, a method of directly forming a release layer on the support and irradiating with an electron beam is mainly used. A release layer containing a curable silicone compound as a main component is provided on a substrate having a matte surface, and then the release layer is superposed and adhered to a support and cured by electron beam irradiation in an adhered state. A method of peeling a base material having a surface, or a release layer containing an electron beam-curable silicone compound as a main component is provided on a support, and then the release layer is placed in close contact with a base material having a matte surface.
A method in which the base material having a matte surface is peeled off after being cured by electron beam irradiation in the adhered state is preferable for forming a uniform matte surface of the release sheet for process.

Examples of the substrate having a matte surface used in the production method of the present invention include a matte surface roll, a matted metal foil, a matted synthetic resin film and the like. The electron beam irradiation direction in the present production method may be either the support side or the mat surface side, but when a mat surface roll is used, it is preferably from the support side from the viewpoint of electron beam absorption loss, and a metal foil is used. When using a sheet-shaped substrate such as a synthetic resin film, prevention of deterioration of the support,
From the viewpoint of electron beam absorption loss, it is preferable to start from the substrate side.

The synthetic resin film may be a polyethylene film, a polypropylene film, a polyethylene terephthalate film or the like, preferably a biaxially oriented polypropylene film or a biaxially oriented polyethylene terephthalate film having good processability and heat resistance.

The thickness of the metal foil and the synthetic resin film is not particularly limited, but is preferably 5 to 300 μm, particularly preferably 10 μm or more from the viewpoint of handling, and the electron beam is applied from the metal foil or the synthetic resin film side. From the viewpoint of electron beam absorption loss upon irradiation, the thickness is preferably 150 μm or less. Further, the method of bringing the support and the release layer into close contact with the metal foil or the synthetic resin film is according to the method which has been widely used in the past, and two methods capable of appropriately crimping the metal foil or the synthetic resin film, the release layer and the paper support. It is easily carried out by passing between rolls.

As a method for providing a release layer containing an electron beam-curable silicone compound as a main component on a support or a matte surface, doctor coat, blade coat, air knife coat, squeeze coat, reverse roll coat, gravure roll and transfer are available. Any method such as roll coating, four or five roll coating, curtain coating, extrusion coating, die coating, slide coating, lip coating, U comma coating and micro gravure coating may be used.

The composition containing the electron beam-curable silicone compound as a main component of the present invention may be applied as it is, or may be applied by mixing an appropriate solvent.

The amount of the composition containing the electron beam-curable silicone compound as a main component, which is applied to the support, varies depending on the type of the support, but is 1 to 20 g / m ² , and more preferably 2
10 to 10 g / m ² . If the amount of the composition is less than this range, it is difficult to form a uniform release layer on a support such as paper, and the releasability deteriorates. Further, even if the amount of the composition exceeds the above range, the characteristics do not change and only the cost increases, which is not preferable.

As the electron beam accelerator used for electron beam curing of the release layer containing an electron beam curable silicone compound as a main component, a curtain system, a scan system or a double scan system can be adopted, but it is relatively inexpensive. The curtain system is preferable because it can easily obtain a large output. The acceleration voltage of the electron beam is 100 to 1000 kV, preferably 150 to 300
The irradiation dose is 0.5 to 10 Mrad, preferably 0.5 to 5 Mrad. If the accelerating voltage is less than 100 kV, the amount of energy transmission is insufficient, and if it exceeds 1000 kV, the energy efficiency is reduced, which is not economical. When the irradiation dose is 0.5 Mrad or less, the curing reaction is insufficient and a tough layer cannot be obtained. When it exceeds 10 Mrad, not only the energy efficiency is lowered, but also the paper support is significantly deteriorated, which is not preferable.

Since the curing by electron beam irradiation is a radical reaction and depends on the oxygen concentration in the atmosphere, it is replaced by an inert gas such as nitrogen, helium, carbon dioxide, etc., and the oxygen concentration is 600 ppm or less, preferably 400 ppm or less. It is preferable to irradiate in an atmosphere which is suppressed.

[0032]

The release sheet for process according to the present invention has a viscosity represented by the general formula 1 of 10 to 200 on at least one surface of the support.
At least one selected from the group consisting of an cps electron-curable silicone compound having a certain proportion or more of acryloyl groups introduced into its molecular terminals and side chains, and an inorganic pigment or organic pigment having an average particle size of 3 μm or less. By providing a release layer formed by applying a release layer containing a pigment as a main component, the acryloyl group does not lose its excellent releasability specific to silicone-based resins due to the aggregating effect during curing of the acryloyl group. For matte surface processes, in which the glossy feeling, which was a drawback of the line curable silicone resin, is reduced, and the scratch resistance, pigment retention, and adhesion of the release layer are significantly improved due to the effect of the acryloyl group introduced into the silicone skeleton. A release sheet is obtained.

[0033]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the content of the present invention is not limited to the Examples.

Example 1 As a base material, an electron beam curable silicone compound 1 having an average compositional formula 3 was applied to cast coated paper having a basis weight of 155 g / m ² (gloss 84, air permeability 4500 seconds, manufactured by Mitsubishi Paper Mills). 10
After thoroughly kneading 0 parts and 300 parts of calcium carbonate having an average particle size of 0.7 μm, 5 g / m using a gravure coater
² was applied, nitrogen substituted (oxygen concentration 200 ppm) electron beam irradiation apparatus was (NHV Corp., curing Tron) guided in the acceleration voltage 200 kV, absorbed dose 3M
An electron beam was irradiated under the condition of rad to cure the electron beam-curable silicone compound to obtain a release sheet for a matte surface.

[Chemical 3] The viscosity of the silicone compound 1 represented by Chemical formula 3 is 1
It is 5 cps.

Example 2 The silicone compound 1 used in the above Example 1 was changed to an electron beam curable silicone compound 2 having an average compositional formula 4,
After thoroughly kneading 100 parts of the silicone resin and 200 parts of calcium carbonate having an average particle size of 0.85 μm, a release sheet for matte process steps was obtained in the same manner as in Example 1.

[Chemical 4] The viscosity of the silicone compound 2 represented by Chemical formula 4 is 6
It is 0 cps.

Example 3 The silicone compound 1 used in the above Example 1 was changed to an electron beam curable silicone compound 3 having an average compositional formula 5,
After thoroughly kneading 100 parts of the silicone resin and 150 parts of calcium carbonate having an average particle diameter of 1.0 μm, a release sheet for a matte surface step was obtained in the same manner as in Example 1.

[Chemical 5] The viscosity of the silicone compound 3 represented by Chemical formula 5 is 1
It is 85 cps.

Example 4 100 parts of the electron beam-curable silicone compound 3 used in the above Example 3 and 50 parts of calcium carbonate having an average particle size of 1.8 μm were thoroughly kneaded, and then the same procedure as in Example 1 was performed. A release sheet for the matte surface was obtained.

Example 5 100 parts of the electron beam-curable silicone compound 3 used in Example 3 above and 30 parts of calcium carbonate having an average particle size of 3.0 μm were thoroughly kneaded, and then the same procedure as in Example 1 was carried out. A release sheet for the matte surface was obtained.

Example 6 Electron beam curable silicone compound 2 used in Example 1
100 parts and calcium carbonate 3 having an average particle size of 0.7 μm
00 parts and Aronix M as electron beam curable resin
After thoroughly kneading 20 parts of 220 (manufactured by Toagosei Kagaku Kogyo Co., Ltd.), a release sheet for steps having a matte surface was obtained in the same manner as in Example 1.

Example 7 Electron beam curable silicone compound 1 used in Example 1
And 100 parts of 80 parts of an acrylic resin powder having an average particle size of 1.0 μm were well kneaded, and then a release sheet for a matte surface was obtained in the same manner as in Example 1.

Comparative Example 1 Example 1 was repeated except that the electron beam curable silicone compound 1 used in the above Example 1 was changed to an electron beam curable silicone compound 4 having an average composition formula 6 and a curing treatment was carried out.
A release sheet for process was obtained in the same manner as in.

[Chemical 6] The viscosity of the silicone compound 4 represented by Chemical formula 6 is 8
cps.

Comparative Example 2 Example 1 was repeated except that the electron beam curable silicone compound 2 used in Example 1 was changed to an electron beam curable silicone compound 5 having an average composition formula 7 and a curing treatment was carried out.
A release sheet for process was obtained in the same manner as in.

[Chemical 7] The viscosity of the silicone compound 5 represented by Chemical formula 7 is 2
It is 50 cps.

Comparative Example 3 Processes were carried out in the same manner as in Example 3 except that the electron beam curable silicone compound 3 used in Example 3 was replaced by an electron beam curable silicone compound 6 having an average composition formula 8. A release sheet for use was obtained.

[Chemical 8] The viscosity of the silicone compound 6 represented by the chemical formula 8 is 7
It is 00 cps.

Comparative Example 4 100 parts of the electron beam-curable silicone compound 1 used in Example 1 above and 350 parts of calcium carbonate having an average particle size of 1.0 μm were thoroughly kneaded, and then the same procedure as in Example 1 was carried out. A release sheet for the matte surface was obtained.

Comparative Example 5 100 parts of the electron beam-curable silicone compound 1 used in Example 1 above and 20 parts of calcium carbonate having an average particle size of 1.0 μm were thoroughly kneaded, and then the same procedure as in Example 1 was performed. A release sheet for the matte surface was obtained.

Comparative Example 6 100 parts of the electron beam-curable silicone compound 1 used in Example 1 above and 100 parts of calcium carbonate having an average particle size of 4.0 μm were thoroughly kneaded, and then the same procedure as in Example 1 was performed. A release sheet for the matte surface was obtained.

Comparative Example 7 100 parts of the electron beam-curable silicone compound 3 used in Example 3 above and 350 parts of calcium carbonate having an average particle size of 1.0 μm were thoroughly kneaded, and then the same procedure as in Example 1 was carried out. A release sheet for the matte surface was obtained.

Comparative Example 8 100 parts of the electron beam-curable silicone compound 3 used in Example 3 above and 20 parts of calcium carbonate having an average particle size of 1.0 μm were thoroughly kneaded, and then the same procedure as in Example 1 was carried out. A release sheet for the matte surface was obtained.

Comparative Example 9 100 parts of the electron beam-curable silicone compound 3 used in Example 3 above and 100 parts of calcium carbonate having an average particle size of 4.0 μm were thoroughly kneaded, and then the same procedure as in Example 1 was performed. A release sheet for the matte surface was obtained.

The following tests were carried out on the release sheets for process obtained in Examples 1 to 7 and Comparative Examples 1 to 9 above.
The respective results are shown in Table 1.

[Peeling Strength] Examples 1 to 7 and Comparative Examples 1 to 9
The release sheet for the step of the process is coated with a urethane paste having the composition shown below in a thickness of 125 μm on the release layer and dried at 120 ° C. for 2 minutes by a dryer, and then the sample is cut into a width of 30 μm.
Peel strength was measured by cutting the film into mm and peeling off the urethane resin coating and the process release sheet at 300 mm / min using a Tensilon universal testing machine (CR7000, manufactured by Orientec Co., Ltd.). (Urethane paste) Urethane resin: Crisbon 6116SL (product of Dainippon Ink and Chemicals, Inc.) 67 parts Methyl ethyl ketone (manufactured by Kanto Chemical Co., Inc.) 33 parts The results are shown in Table 1.

[Glossiness] The 60 ° glossiness of the release sheets for processes of Examples 1 to 7 and Comparative Examples 1 to 9 was measured, and the results are shown in Table 1.

[Mat Agent Retention] The transferability of the mat agent to the transfer surface was evaluated by visually observing the urethane transfer surface prepared in the above peel strength test. The case where the transfer was good was represented by ◯, and the case where migration of the matting agent was clearly observed was represented by x.

[Transfer surface glossiness] The matte surface of the urethane transfer surface prepared in the above peel strength test was visually evaluated for uniformity and matte feeling.

[Smoothness of Transfer Surface] The smoothness of the urethane transfer surface prepared in the above matte agent retention test was visually evaluated. Asperities that are evenly applied at the particle size level of the matting agent, and are much larger than those of the matting agent (such as swelling of fibers and paper)
Those that did not exist were evaluated as good, and those in which the transfer on the mat surface was non-uniform, or where the transfer surface had irregularities or shading much larger than the particle size of the matting agent were considered defective.

[Scratch resistance] The surfaces of the matte surface release sheets obtained in the examples and comparative examples were rubbed several times with gauze, and then with a urethane paste in the same manner as in the peel strength test. Created a matte surface. By visually observing the change in the matte feeling of the matte surface obtained, those with no change in the matte feeling of the rubbed portion were regarded as good scratch resistance, and those with the change of matte feeling in the rubbed portion The scratch resistance was evaluated as poor.

[0057]

[Table 1]

Evaluation: The release sheet for matte surface process prepared in the example has sufficient mattability and low gloss even when an electron beam curable resin is used, and also retainability of matting agent and characteristics of transfer surface. It is a good one. When the silicone resin of the present invention is cured by electron beam irradiation, due to the aggregating effect of the acryloyl group at the time of curing, it does not impair the excellent releasability peculiar to the silicone resin, and is A matte release sheet for a process, in which the glossy feeling, which was a defect, is reduced, and due to the effect of the acryloyl group introduced into the silicone skeleton, the scratch resistance, pigment retention, and adhesiveness of the release layer are remarkably improved. Is.
Since it is not heated at the time of production, curling and wrinkles are not generated, pinholes are not generated by the solvent, and pinholes are not generated due to excessive penetration of the silicone resin, and proper peeling is obtained.

The release sheet for process prepared in the comparative example has a problem in the retention of the matting agent when the viscosity of the silicone resin is low, the content of the matting agent is high, or the average particle diameter of the matting agent is large. However, the smoothness and scratch resistance of the transfer surface are not good. When the viscosity of the silicone resin is high, or when the content of the matting agent is small, a matte surface is not formed, but a glossy and glossy surface is obtained.

[0060]

As is apparent from Table 1, the present invention provides a means for efficiently producing a release sheet for a process having a matte surface, which is of great industrial value.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location B32B 27/20 A 6122-4F C09J 7/02 JKV 6770-4J D06N 3/00 7141-4F (72 ) Inventor Shinji Irifune 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (2)

[Claims] 1. The viscosity represented by the average composition formula 1 (general formula 1) on at least one surface of the support is 10 to 200 cps.
Electron beam curable silicone compound with an average particle size of 3
A release sheet for a matte surface process, which is formed by applying a release layer containing as a main component at least one pigment selected from organic pigments and inorganic pigments having a thickness of at most μm. [Chemical 1] 2. In the release sheet for the process, 3 parts of the pigment are added to 100 parts of the electron beam-curable silicone compound.
The release sheet for a matte surface process according to claim 1, wherein a release layer mixed in a ratio of 0 to 300 parts is applied.