JP2014054811A - Release sheet and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a release sheet which not only excel in releasability from an adhesive material but prevents blocking even when the release sheet is wound up into a roll, and which can be easily produced.SOLUTION: The release sheet comprises: a resin layer 1; and a resin layer 2, each of which is layered in this order on a substrate. The resin layer 1 comprises: 100 parts by mass of an acid-modified polybutadiene and/or an acid-modified polyisoprene; and 1 to 50 parts by mass of a crosslinking agent containing at least one compound selected from an oxazoline compound, a carbodiimide compound and a melamine compound. The resin layer 1 has a thickness of 0.01 to 0.3 μm. The resin layer 2 comprises 100 parts by mass of an acid-modified polyolefin resin and 1 to 50 parts by mass of a crosslinking agent containing at least one compound selected from an oxazoline compound, a carbodiimide compound and a melamine compound. The resin layer 2 has a thickness of 0.01 to 0.3 μm.

Description

  The present invention relates to a release sheet and a manufacturing method thereof.

In general, the release sheet is bonded to the surface of the pressure-sensitive adhesive layer in order to protect the surface of the pressure-sensitive adhesive layer such as a pressure-sensitive adhesive label or a pressure-sensitive adhesive film until use.
The release sheet has a release layer provided on the surface of the substrate, and silicone release agents that have excellent release properties for various adhesives are most often used for the release layer. ing.
However, in a release sheet in which a silicone release agent is used for the release layer, it is known that a low molecular weight silicone compound in the release layer moves to the surface of the pressure-sensitive adhesive. Since the silicone compound transferred to the pressure-sensitive adhesive layer is vaporized and becomes a silicon oxide compound, the pressure-sensitive adhesive bonded to the release sheet in which the silicone-based release agent is used for the release layer is used for electronic parts and the like. It is pointed out that this leads to defects and failures of electronic components.

  In order to solve the above problems, a release sheet that does not use a silicone release agent has been proposed. Patent Document 1 proposes a release sheet coated with a release agent using an acid-modified polyolefin resin. Patent Document 2 discloses a release layer by applying a release agent containing polybutadiene and irradiating with ultraviolet rays. A release sheet having a shape has been proposed.

However, although the release sheet of Patent Document 1 shows good release properties for various adherends, the release sheet is heavy for the adhesive and is handled when the release sheet is released from the adhesive sheet. In some cases, the surface of the pressure-sensitive adhesive of the pressure-sensitive adhesive sheet becomes rough when the release sheet is peeled off, and the smoothness and transparency of the pressure-sensitive adhesive sheet surface may be impaired.
In addition, the release sheet of Patent Document 2 has good release properties with respect to the pressure-sensitive adhesive, but since the release layer resin is soft, when the release sheet is rolled up, the release layer May be blocked and cannot be unwound from the roll during use. Further, the release layer needs to be cured by irradiation with ultraviolet rays, and special equipment and processes are required in production. Furthermore, in order to provide the release layer, this release sheet uses a liquid material in which a resin is dissolved in an organic solvent, which is not preferable from the viewpoint of the environment.

JP 2009-101680 A JP-A-2005-212121

  In view of these problems, the present invention seeks to provide a release sheet that is not only excellent in releasability with an adhesive material but also does not cause blocking when rolled up, and is easy to manufacture. Is.

As a result of intensive studies to solve the above problems, the present inventor has, on the substrate, at least one selected from acid-modified polyisoprene and / or acid-modified polyisoprene and an oxazoline compound, carbodiimide compound, or melamine compound. A resin layer 1 containing a cross-linking agent is provided, and a resin layer 2 containing a cross-linking agent containing at least one selected from an acid-modified polyolefin resin, an oxazoline compound, a carbodiimide compound, and a melamine compound on the resin layer 1. It has been found that the release sheet laminated with is excellent in releasability from the pressure-sensitive adhesive material, is excellent in blocking resistance when rolled up in a roll shape, and can be easily produced, and has reached the present invention.
That is, the gist of the present invention is as follows.
(1) A release sheet in which a resin layer 1 and a resin layer 2 are laminated in this order on a base material, the resin layer 1 comprising 100 parts by mass of acid-modified polybutadiene and / or acid-modified polyisoprene, and oxazoline 1 to 50 parts by mass of a crosslinking agent containing at least one selected from a compound, a carbodiimide compound, and a melamine compound, the thickness of the resin layer 1 is 0.01 to 0.3 μm, and the resin layer 2 is an acid-modified polyolefin. 100 mass parts of resin, 1-50 mass parts of crosslinking agents containing at least one chosen from an oxazoline compound, a carbodiimide compound, and a melamine compound are contained, and the thickness of the resin layer 2 is 0.01-0.3 micrometer. Release sheet characterized by.
(2) The release sheet according to (1), wherein the peel strength between the resin layer 2 and the acrylic adhesive material is 0.5 N / cm or less.
(3) The release sheet according to (1) or (2), wherein the substrate is any one of a resin material, paper, synthetic paper, cloth, metal material, and glass material.
(4) The release sheet according to (3), wherein the resin material is a polyester resin film.
(5) A method for producing the release sheet according to (1) above, wherein at least one selected from 100 parts by mass of acid-modified polybutadiene and / or acid-modified polyisoprene, an oxazoline compound, a carbodiimide compound, and a melamine compound The liquid 1 dispersed in an aqueous medium containing 1 to 50 parts by mass of a cross-linking agent containing one is applied on a substrate and dried to form a resin layer 1, and then 100 parts by mass of an acid-modified polyolefin resin And a liquid 2 dispersed in an aqueous medium containing 1 to 50 parts by mass of a cross-linking agent containing at least one selected from an oxazoline compound, a carbodiimide compound, and a melamine compound is applied on the resin layer 1 and then dried. A method for producing a release sheet, wherein the resin layer 2 is formed.

  The release sheet of the present invention has a resin layer 1 containing a cross-linking agent containing acid-modified polybutadiene and / or acid-modified polyisoprene and at least one selected from an oxazoline compound, a carbodiimide compound, and a melamine compound on a base material. Furthermore, on the resin layer 1, by laminating an acid-modified polyolefin resin and a resin layer 2 containing a crosslinking agent containing at least one selected from an oxazoline compound, a carbodiimide compound, and a melamine compound, It is excellent in releasability and does not cause blocking even when rolled up. The release sheet of the present invention can be easily produced by applying a liquid material in which a resin is dispersed in an aqueous medium to a substrate and drying.

Hereinafter, the present invention will be described in detail.
The release sheet of this invention has a base material and the resin layer 1 and the resin layer 2 which were provided on this base material. The resin layer 1 contains acid-modified polybutadiene and / or acid-modified polyisoprene and a crosslinking agent.

  The butadiene skeleton in the acid-modified polybutadiene may have any structure of 1,2-vinyl type, 1,4-trans type, or 1,4-cis type, and has two or more types of these structures. The ratio is not particularly limited.

As the acid-modified component of the acid-modified polybutadiene, an unsaturated carboxylic acid can be used, and specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride are preferable and easily available. To maleic acid and maleic anhydride are particularly preferred.
The content of the unsaturated carboxylic acid in the acid-modified polybutadiene is 1 to 400 mgKOH / g as the acid value of the acid-modified polybutadiene, from the viewpoint of reaction with the crosslinking agent and from the viewpoint of easily obtaining an aqueous dispersion of acid-modified polybutadiene described later. Is preferable, 30 to 300 mgKOH / g is more preferable, 50 to 300 mgKOH / g is more preferable, and 70 to 250 mgKOH / g is particularly preferable from the viewpoint of adhesion to a substrate and releasability.
When the acid value of the acid-modified polybutadiene is less than 1 mgKOH / g, the resin layer not only has a possibility of transferring to the adhesive surface due to a decrease in adhesion to the base material, but also an aqueous dispersion of the acid-modified polybutadiene. Getting a body can be difficult. On the other hand, when the acid value exceeds 400 mgKOH / g, there is a possibility that the releasability is lowered due to strong adhesion with the adhesive.
The unsaturated carboxylic acid component only needs to be copolymerized in the acid-modified polybutadiene, and the form thereof is not limited, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization (graft modification). .

  The number average molecular weight of the acid-modified polybutadiene is preferably 200 to 20000, and more preferably 500 to 10,000. The number average molecular weight can be measured using gel permeation chromatography (GPC).

  The acid-modified polybutadiene is obtained by modifying polybutadiene with an unsaturated carboxylic acid, but it is convenient to use a commercially available one. Examples of commercially available products include maleated butadiene manufactured by Nippon Soda Co., Ltd. (BN-1010, etc.), maleated butadiene manufactured by JX Nippon Oil & Energy Corporation (M-1000-20, M-1000-80, M-2000-20). , M-2000-80, etc.) and maleated butadiene (polyvest OC800S, etc.) manufactured by Evonik Degussa.

  On the other hand, the skeleton of isoprene in the acid-modified polyisoprene may have any structure of 1,2-vinyl type, 3,4-vinyl type, 1,4-cis type, 1,4-trans type, You may have 2 or more types of these structures.

As an acid-modified component of the acid-modified polyisoprene, an unsaturated carboxylic acid can be used. Specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride are preferable and easily available. Therefore, maleic acid and maleic anhydride are particularly preferable.
The content of the unsaturated carboxylic acid in the acid-modified polyisoprene is 1 to 1 as the acid value of the acid-modified polyisoprene, from the viewpoint of reaction with the crosslinking agent and from the viewpoint of easily obtaining an aqueous dispersion of acid-modified polyisoprene described later. 400 mgKOH / g is preferable, 3-300 mgKOH / g is more preferable, 4-200 mgKOH / g is more preferable, and 5-100 mgKOH / g is especially preferable from a viewpoint of adhesiveness with a base material or mold release property.
When the acid value of the acid-modified polyisoprene is less than 1 mgKOH / g, the resin layer not only has a possibility of transferring to the pressure-sensitive adhesive surface due to a decrease in adhesion to the substrate, It may be difficult to obtain an aqueous dispersion. On the other hand, when the acid value exceeds 400 mgKOH / g, there is a possibility that the releasability is lowered due to strong adhesion with the adhesive.
Further, the unsaturated carboxylic acid component only needs to be copolymerized in the acid-modified polyisoprene, and the form thereof is not limited, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization (graft modification). It is done.

  The number average molecular weight of the acid-modified polyisoprene is preferably 200 to 100,000, more preferably 3000 to 70000, and still more preferably 10,000 to 50000. The number average molecular weight can be measured using gel permeation chromatography (GPC).

  The acid-modified polyisoprene is obtained by modifying polyisoprene with an unsaturated carboxylic acid, but it is easy to use a commercially available one. As a commercially available product, for example, maleic anhydride-modified polyisoprene “LIR-403”, “LIR-410” manufactured by Kuraray Co., Ltd. can be used.

  The resin layer 1 of the release sheet of the present invention contains a crosslinking agent together with the acid-modified polybutadiene and / or acid-modified polyisoprene. As the crosslinking agent, a compound having a plurality of functional groups in the molecule that react with the acid-modified component of acid-modified polybutadiene and / or acid-modified polyisoprene is used. From the viewpoint of reactivity, an oxazoline compound, a carbodiimide compound, a melamine compound It is necessary that the crosslinking agent contains at least one selected from the group consisting of:

The oxazoline compound is not particularly limited as long as it has two or more oxazoline groups in the molecule. For example, 2,2'-bis (2-oxazoline), 2,2'-ethylene-bis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis (2-oxazoline) , A compound having an oxazoline group such as bis (2-oxazolinylcyclohexane) sulfide, and an oxazoline group-containing polymer. These 1 type (s) or 2 or more types can be used. Among these, an oxazoline group-containing polymer is preferable because of ease of handling.
The oxazoline group-containing polymer is obtained by polymerizing an addition polymerizable oxazoline such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline. Other monomers may be copolymerized as necessary. The polymerization method of the oxazoline group-containing polymer is not particularly limited, and various known polymerization methods can be employed. An example of a commercially available oxazoline group-containing polymer is EPOCROSS series manufactured by Nippon Shokubai Co., Ltd. Specific product names include, for example, water-soluble type “WS-500”, “WS-700”; emulsion type “K-1010E”, “K-1020E”, “K-1030E”, “K-” 2010E "," K-2020E "," K-2030E "and the like.

The carbodiimide compound is not particularly limited as long as it has at least two or more carbodiimide groups in the molecule. For example, compounds having a carbodiimide group such as p-phenylene-bis (2,6-xylylcarbodiimide), tetramethylene-bis (t-butylcarbodiimide), cyclohexane-1,4-bis (methylene-t-butylcarbodiimide) And polycarbodiimide which is a polymer having a carbodiimide group. These 1 type (s) or 2 or more types can be used. Among these, polycarbodiimide is preferable from the viewpoint of ease of handling.
The method for producing polycarbodiimide is not particularly limited. Polycarbodiimide can be produced, for example, by a condensation reaction involving decarbonization of an isocyanate compound. The isocyanate compound is not limited, and any of aliphatic isocyanate, alicyclic isocyanate, and aromatic isocyanate may be used. The isocyanate compound may be copolymerized with a polyfunctional liquid rubber or polyalkylene diol as necessary. As a commercially available product of polycarbodiimide, there is a carbodilite series manufactured by Nisshinbo. Specific products include, for example, water-soluble type “SV-02”, “V-02”, “V-02-L2”, “V-04”; emulsion type “E-01”, “E -02 "; organic solution type" V-01 "," V-03 "," V-07 "," V-09 "; solvent-free type" V-05 "and the like.

A melamine compound is a compound in which an amino group is bonded to three carbon atoms of a triazine ring, and the amino group of so-called melamine [1,3,5-triazine-2,4,6-triamine] is subjected to various modifications. And includes those in which a plurality of triazine rings are condensed. As the type of modification, one in which some of the hydrogen atoms of three amino groups are alkylated or methylolated is widely used. In general, methylolated or unsubstituted hydrogen atoms are more reactive than alkylated ones, and an appropriate type of melamine compound can be selected depending on the application. Among them, the average number of condensed triazine rings is 3 or less, and at least one amino group is methylol-substituted, and these are dispersible in an aqueous medium and reactive with a resin. Is excellent.
Examples of commercially available melamine compounds include Cymel series manufactured by Nippon Cytec Industries, Sumima manufactured by Sumitomo Chemical Co., and becamine manufactured by DIC.

  The total content of the oxazoline compound, carbodiimide compound, and melamine compound as the crosslinking agent needs to be 1 to 50 parts by mass with respect to 100 parts by mass in total of the acid-modified polybutadiene and the acid-modified polyisoprene. The amount is more preferably 30 parts by mass, and further preferably 3 to 20 parts by mass. If the content is less than 1 part by mass, the effect of addition is poor, and the releasability may decrease over time, and there is a possibility of blocking when wound into a roll. If the content exceeds 50 parts by mass, the releasability may decrease. Two or more kinds of oxazoline compounds, carbodiimide compounds, and melamine compounds can be selected and used at the same time. When they are used at the same time, it is sufficient that the total amount thereof satisfies the above-described content range.

The release sheet of this invention has the resin layer 2 with the said resin layer 1, and the resin layer 2 contains acid-modified polyolefin resin and a crosslinking agent.
Examples of the acid-modified component of the acid-modified polyolefin resin include an unsaturated carboxylic acid component. Examples of unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. It is done. Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable from the viewpoint of dispersion stability of the resin, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferable.
The amount of the acid-modified component is not particularly limited, but is preferably 1 to 10% by mass of the acid-modified polyolefin resin, more preferably 1 to 7% by mass, and 2 to 5% by mass. It is particularly preferred. When the acid modification is not performed, sufficient adhesion between the resin layer 1 and the resin layer 2 may not be obtained, and the resin layer 2 may contaminate the pressure-sensitive adhesive surface. Furthermore, there is a tendency that aqueous dispersion as described later becomes difficult. On the other hand, when the amount of the acid-modified component is too large, the peel strength between the resin layer 2 and the adhesive material may increase.

  Although the olefin component which is the main component of the acid-modified polyolefin resin is not particularly limited, an alkene having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene and 1-hexene is preferable. . A mixture thereof may be used. Among these, alkene having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene is more preferable, ethylene and propylene are further preferable, and ethylene is most preferable.

  The acid-modified polyolefin resin preferably contains a (meth) acrylic acid ester component for the purpose of improving the adhesion to the resin layer 1. When a (meth) acrylic acid ester component is included, the content is preferably 0.5 to 40% by mass, more preferably 1 to 20% by mass, and 3 to 10% by mass. Further preferred. Examples of the (meth) acrylic acid ester component include an esterified product of (meth) acrylic acid and an alcohol having 1 to 30 carbon atoms, and (meth) acrylic acid and carbon number 1 from the viewpoint of easy availability. Esterified products with ˜20 alcohols are preferred. Specific examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid. Examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Mixtures of these may be used. Among these, from the viewpoint of adhesion to the substrate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, octyl acrylate are more preferable, ethyl acrylate, More preferred is butyl acrylate, and particularly preferred is ethyl acrylate. In addition, “(meth) acrylic acid˜” means “acrylic acid˜ or methacrylic acid˜”.

  Each component constituting the acid-modified polyolefin resin may be copolymerized in the acid-modified polyolefin resin, and the form thereof is not limited. Examples of the state of copolymerization include random copolymerization, block copolymerization, and graft copolymerization (graft modification).

The melting point of the acid-modified polyolefin resin is preferably 80 to 150 ° C, more preferably 85 to 130 ° C, and further preferably 90 to 100 ° C. When the melting point exceeds 150 ° C., a treatment at a high temperature is required to form the release layer 2, and when the melting point is less than 80 ° C., the releasability may be remarkably lowered.
The Vicat softening point of the acid-modified polyolefin resin is preferably 50 to 130 ° C, more preferably 53 to 110 ° C, and more preferably 55 to 90 ° C. When the Vicat softening point is less than 50 ° C., the releasability decreases, and when it exceeds 130 ° C., a high temperature treatment may be required for forming the release layer 2.
The melt flow rate of the acid-modified polyolefin resin is preferably 1 to 1000 g / 10 minutes at 190 ° C. and 2160 g load, more preferably 1 to 500 g / 10 minutes, and 2 to 300 g / 10 minutes. Is more preferable, and 2 to 200 g / 10 min is particularly preferable. When the amount is less than 1 g / 10 minutes, it is difficult to produce a resin and it is difficult to obtain an aqueous dispersion. If it exceeds 1000 g / 10 min, the adhesion to the release layer 1 may be reduced, and the release layer 2 may easily migrate to the adherend.

  Examples of the trade name of the acid-modified polyolefin resin that can be used in the present invention include Bondine series, which is a maleic anhydride polyolefin resin manufactured by Arkema. Specific product names include “LX-4110”, “HX-8210”, “HX-8290”, “AX-8390”, and the like.

The resin layer 2 of the release sheet of the present invention contains a crosslinking agent together with the acid-modified polyolefin resin. As the crosslinking agent contained in the resin layer 2 of the present invention, a compound having a plurality of functional groups in the molecule that react with the acid component of the acid-modified polyolefin resin is used. From the viewpoint of reactivity, the crosslinking agent in the resin layer 1 is used. It is necessary that the crosslinking agent contains at least one selected from oxazoline compounds, carbodiimide compounds, and melamine compounds.
Further, the total content of the oxazoline compound, carbodiimide compound, and melamine compound as the crosslinking agent should be 1 to 50 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin, similarly to the crosslinking agent in the resin layer 1. It is more preferable that it is 2-30 mass parts, and it is further more preferable that it is 3-20 mass parts. If the content is less than 1 part by mass, the effect of addition is poor, the release properties may deteriorate with time, the heat resistance may be insufficient, and there is a risk of blocking when wound into a roll. If the content exceeds 50 parts by mass, the releasability may decrease. Two or more kinds of oxazoline compounds, carbodiimide compounds, and melamine compounds can be selected and used at the same time. When they are used at the same time, it is sufficient that the total amount thereof satisfies the above-described content range.

The release sheet of the present invention is a sheet obtained by laminating the resin layer 1 and the resin layer 2 in this order on a base material.
In the present invention, the thickness of the resin layer 1 and the resin layer 2 needs to be 0.01 to 0.3 μm, respectively.
When the thickness of the resin layer 1 is less than 0.01 μm, sufficient releasability may not be obtained. On the other hand, if the thickness of the resin layer 1 exceeds 0.3 μm, blocking may occur when the release sheet is rolled up.
Moreover, when the thickness of the resin layer 2 is less than 0.01 μm, blocking may occur when the release sheet is rolled up. On the other hand, when the thickness of the resin layer 2 exceeds 0.3 μm, sufficient releasability may not be obtained. It is also possible to control the releasability from the adhesive material by controlling the thickness of the resin layer 2.

  Examples of the base material of the release sheet include those formed of resin material, paper, synthetic paper, cloth, metal material, glass material and the like. Although the thickness of a base material is not specifically limited, Usually, what is necessary is just 1-1000 micrometers, 1-500 micrometers is preferable, 10-200 micrometers is more preferable, and 25-100 micrometers is especially preferable.

  Examples of resin materials that can be used for the substrate include polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polylactic acid (PLA) as thermoplastic resins; polyolefin resins such as polypropylene; polystyrene resins; Polyamide resin such as nylon 6, poly-m-xylylene adipamide (MXD6 nylon); polycarbonate resin; polyacrylonitrile resin; polyimide resin; multilayer of these resins (for example, nylon 6 / MXD6 nylon / nylon 6) , Nylon 6 / ethylene-vinyl alcohol copolymer / nylon 6) and mixtures. The resin material may be stretched. Among them, the base material is preferably a polyester resin film excellent in mechanical properties and thermal properties, and is preferably a polyethylene terephthalate film from the viewpoint of being inexpensive and easily available.

  The film made of the thermoplastic resin may contain a known additive or stabilizer, such as an antistatic agent, a plasticizer, a lubricant, or an antioxidant. The thermoplastic resin film may have a surface subjected to a corona treatment, a plasma treatment, an ozone treatment, a chemical treatment, a solvent treatment, or the like as a pretreatment in order to improve adhesion when laminated with other materials. Moreover, silica, alumina, etc. may be vapor-deposited, and other layers, such as a barrier layer, an easily bonding layer, an antistatic layer, and an ultraviolet absorption layer, may be laminated.

  Examples of paper that can be used as the substrate include Japanese paper, kraft paper, liner paper, art paper, coated paper, carton paper, glassine paper, and semi-glassine paper. The paper may be provided with a sealing layer or the like.

  The structure of the synthetic paper that can be used as the substrate is not particularly limited, and may be a single layer structure or a multilayer structure. As a multilayer structure, for example, a two-layer structure of a base material layer and a surface layer, a three-layer structure in which a surface layer exists on the front and back surfaces of the base material layer, and another resin film layer exists between the base material layer and the surface layer. A multilayer structure can be exemplified. Each layer may or may not contain an inorganic or organic filler. A microporous synthetic paper having a large number of fine voids can also be used.

  Examples of the cloth that can be used as the substrate include fibers made of the above-described synthetic resin, nonwoven fabrics made of natural fibers such as cotton, silk, and linen, woven cloth, and knitted cloth. Examples of the metal material that can be used as the substrate include metal foils such as aluminum foil and copper foil, and metal plates such as aluminum plate and copper plate. Examples of the glass material that can be used as the substrate include a glass plate and a cloth made of glass fiber.

  In the release sheet of the present invention in which the resin layer 1 and the resin layer 2 are laminated in this order on the base material, the resin layer 2 is composed of the resin layer 2 and the acrylic adhesive after the acrylic adhesive material is attached. The peel strength between the materials can be 0.5 N / cm or less, more preferably 0.4 N / cm or less, still more preferably 0.3 N / cm or less, and most preferably 0.2 N / cm. cm or less. When peeling strength exceeds 0.5 N / cm, it may become difficult to use as a release sheet for adhesive materials. In addition, the peeling strength as used in the field of this invention is peeling when the adhesive tape mentioned later is affixed on the resin layer 2 side of a release sheet, and it peels by pulling an adhesive tape in the direction of 180 degree | times at a speed | rate of 300 mm / min. Refers to strength.

  In the present invention, the method for laminating the release layers 1 and 2 on the base material is not particularly limited, and for example, it is selected from 100 parts by mass of acid-modified polybutadiene and / or acid-modified polyisoprene, oxazoline compound, carbodiimide compound, and melamine compound. A liquid 1 containing 1 to 50 parts by mass of a crosslinking agent containing at least one of the above and a medium is formed, the liquid 1 is applied to a substrate, and the medium is dried to form a resin layer 1; A liquid 2 containing 100 parts by mass of an acid-modified polyolefin resin, 1 to 50 parts by mass of a crosslinking agent containing at least one selected from an oxazoline compound, a carbodiimide compound, and a melamine compound, and a medium is prepared. The method of applying the resin layer 1 and drying it to form the resin layer 2 makes it easy to make the release layers 1 and 2 uniform in thickness, enabling mass production. In preferred. Furthermore, it is preferable to use an aqueous medium as a medium from the viewpoint of improving the working environment.

  A method of mixing acid-modified polybutadiene and / or acid-modified polyisoprene and a crosslinking agent in order to prepare the liquid material 1, and a method of mixing acid-modified polyolefin resin and a crosslinking agent in order to prepare the liquid material 2. Is not particularly limited as long as each component is uniformly mixed in the liquid medium. For example, a method in which a dispersion or solution of a crosslinking agent is added to and mixed with a dispersion of acid-modified polybutadiene and / or modified polyisoprene or a dispersion of acid-modified polyolefin resin, or acid-modified polybutadiene and / or acid-modified polyisoprene. And a method of liquefying a mixture of a crosslinking agent and an acid-modified polyolefin resin and a crosslinking agent.

  A method for obtaining an aqueous dispersion by dispersing acid-modified polybutadiene and / or acid-modified polyisoprene or acid-modified polyolefin resin in an aqueous medium is not particularly limited. For example, acid-modified polybutadiene and / or acid-modified polybutadiene is sealed in a sealable container. Examples include a method of preparing an aqueous dispersion by charging raw materials such as isoprene, acid-modified polyolefin resin, an organic solvent, and water, and stirring while maintaining the temperature in the tank at about 40 to 150 ° C. For example, the method described in the pamphlet of International Publication No. 02/055598 can be cited, and by neutralizing acid-modified polybutadiene and / or acid-modified polyisoprene or acid-modified polyolefin resin with a basic compound in an aqueous medium, A good aqueous dispersion is obtained.

It is preferable that the said basic compound is volatile from the point of the water resistance of the coating film after mold release layer formation. In the present invention, “volatile” means that the boiling point at normal pressure is 250 ° C. or less. When the boiling point exceeds 250 ° C., it becomes difficult to disperse the basic compound from the resin coating film by drying, and the water resistance of the coating film may decrease.
Volatile basic compounds include ammonia, triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxy. Propylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine etc. can be mentioned.

The aqueous medium as used in the field of this invention is a medium which has water as a main component, and may contain the organic solvent and the water-soluble basic compound as needed.
Examples of organic solvents include diethyl ketone (3-pentanone), methyl propyl ketone (2-pentanone), methyl isobutyl ketone (4-methyl-2-pentanone), 2-hexanone, 5-methyl-2-hexanone, and 2-to. Ketones such as butanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, benzene, Solvesso 100, Solvesso 150, butane, pentane, hexane, cyclohexane, heptane Aliphatic hydrocarbons such as octane and nonane, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, Halogen-containing compounds such as p-dichlorobenzene, acetic acid Esters such as chill, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, γ-butyrolactone, isophorone, etc. Examples include hydrophilic organic solvents described below.

Specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert. -Amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc. Alcohols, ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as acetone and methyl ethyl ketone, methyl acetate, acetic acid-n-propyl, ethyl acetate Propyl acetate -tert- butyl, methyl propionate, ethyl propionate, dimethyl carbonate, etc., dimethylformamide, dimethylacetamide, diacetone alcohol, acetonitrile, and the like.
Specific examples of the water-soluble basic compound include ammonia, diethylamine, triethylamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-diethanolamine, 3-methoxypropyl. Examples thereof include organic amine compounds such as amine, 3-diethylaminopropylamine, and dimethylaminopropylamine.

  The number average particle diameter (hereinafter referred to as mn) of the acid-modified polybutadiene and / or acid-modified polyisoprene particles and acid-modified polyolefin resin particles in the aqueous dispersion is the storage stability of the aqueous dispersion, the transparency of the coating film, and 30 ° C. In terms of improving the film forming property at the following low temperature, 0.5 μm or less is preferable, 0.005 to 0.3 μm is more preferable, 0.01 to 0.2 μm is further preferable, and 0.01 to 0 is preferable. .1 μm is particularly preferred. Furthermore, regarding a weight average particle diameter (henceforth, mw), 1 micrometer or less is preferable, 0.01-0.5 micrometer is more preferable, 0.01-0.2 micrometer is especially preferable.

  A liquid 1 or liquid 2 is obtained by adding and mixing a dispersion or solution of a crosslinking agent to an aqueous dispersion of acid-modified polybutadiene and / or modified polyisoprene or an aqueous dispersion of acid-modified polyolefin resin obtained by the above method. Can be obtained.

  The solid content in the liquids 1 and 2 used in the present invention can be appropriately selected depending on the lamination conditions, the intended thickness and performance, and is not particularly limited. However, the solid content is preferably 1 to 60% by mass, and 5 to 30% by mass in order to keep the viscosities of the liquids 1 and 2 moderate and to form the good release layers 1 and 2. More preferred.

  In addition, liquids 1 and 2, as required, various agents such as leveling agents, antifoaming agents, anti-waxing agents, antistatic agents, pigment dispersants, UV absorbers, titanium oxide, zinc white, carbon black, etc. Other pigments or dyes may be added. In addition, organic or inorganic compounds other than those described above can be added to the liquid materials 1 and 2 as long as the stability of the liquid materials 1 and 2 is not impaired.

In the present invention, the method for laminating the resin layer 1 and the resin layer 2 on the base material is not particularly limited, and the liquid material 1 is applied onto the base material as described above and dried to form the resin layer 1. Then, it can be easily obtained industrially by a production method in which the liquid material 2 is applied to the resin layer 1 and then dried to form the resin layer 2.
That is, using the liquid 1 or liquid 2 as described above, known methods such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, Uniform release layer by applying uniformly to the surface of the substrate or the surface of the resin layer 1 by brushing, etc., and setting it near room temperature as necessary, followed by drying treatment or heat treatment for drying. 1 can be formed on the base material and the uniform resin layer 2 can be formed on the resin layer 1 in close contact with each other.

  After forming the resin layer 1 and the resin layer 2 on the substrate, the acid-modified polyolefin of the resin layer 2 is used to promote the reaction between the acid-modified polybutadiene and / or acid-modified polyisoprene of the resin layer 1 and the crosslinking agent. In order to promote the reaction between the resin and the crosslinking agent, an aging treatment may be performed in an environment controlled at a constant temperature. The aging temperature is preferably relatively low from the viewpoint of reducing damage to the substrate, and is preferably treated at a high temperature from the viewpoint of allowing the reaction to proceed sufficiently and quickly. Aging is preferably performed at 20 to 100 ° C, more preferably at 30 to 70 ° C, and even more preferably at 40 to 60 ° C.

  The release sheet of the present invention can be applied to an adhesive material in which an adhesive is laminated on both sides of a substrate, and may be applied to an adhesive material in which an adhesive is laminated on one side of a substrate. In practice, it can be applied to those used in the form of pressure-sensitive adhesive sheets, adhesive sheets, pressure-sensitive adhesive tapes, adhesive tapes and the like. The component and base material of an adhesive are not specifically limited. Examples of the adhesive include acrylic adhesives, natural rubber adhesives, synthetic rubber adhesives, silicone adhesives, urethane adhesives, and the like. The pressure-sensitive adhesive may contain a tackifier such as rosin, coumarone-indene, terpene, petroleum, styrene, phenol, xylene. Moreover, additives, such as a softening agent, a crosslinking agent, anti-aging agent, and a filler, may be included as needed. Examples of the base material in the adhesive material include the above-described paper, cloth, and resin material. Moreover, it is not necessary to use a base material.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

(1) Acid value of resin 0.15 g of resin was dissolved in 20 ml of tetrahydrofuran, titrated with KOH aqueous solution using cresol red as an indicator, and the acid value (mg KOH / mg) of resin was calculated from the number of mg of KOH consumed for neutralization. g) was determined.

(2) Solid Content Concentration of Aqueous Dispersion An appropriate amount of the aqueous dispersion was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight to obtain the solid content concentration.

(3) Average particle diameter of aqueous dispersion Using a Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340, dynamic light scattering method) manufactured by Nikkiso Co., Ltd., the number average particle diameter (mn) and the weight average particle diameter (mw) Asked. Here, the refractive index of the resin used for calculating the particle diameter was set to 1.50.

(4) Thickness of Resin Layers 1 and 2 Regarding the thickness of the resin layer 1, after laminating the resin layer 1 on the substrate, the entire thickness is measured with a contact-type film thickness meter, and the measured value of the substrate Obtained by reducing the thickness. Moreover, about the thickness of the resin layer 2, after laminating | stacking the resin layer 2 on the resin layer 1, the whole thickness is measured with a contact-type film thickness meter, and the thickness of a base material and the thickness of the resin layer 1 are measured. And subtracted.

(5) Peel strength (at room temperature)
A polyester pressure-sensitive adhesive tape (Nitto Denko Corporation, No. 31B / acrylic pressure-sensitive adhesive) having a width of 50 mm and a length of 150 mm is pressure-bonded to the resin layer 2 side of the obtained release sheet with a rubber roll, and a peel strength measurement sample It was. The peel strength between the adhesive tape and the release sheet of this peel strength measurement sample was measured with a tensile tester (manufactured by Intesco, precision universal material tester, type 2020) in a thermostatic chamber at 25 ° C. The peeling angle was 180 degrees and the peeling speed was 300 mm / min.

(6) Peel strength (after 70 ° C-24 hours)
A polyester adhesive tape (Nitto Denko Corporation, No. 31B / acrylic adhesive) having a width of 50 mm and a length of 150 mm was pressure-bonded to the resin layer 2 side of the obtained release sheet with a rubber roll to prepare a sample. The sample was sandwiched in the form of a metal plate / rubber plate / sample / rubber plate / metal plate and allowed to stand in an atmosphere of 2 kPa load and 70 ° C. for 24 hours to obtain a sample for peel strength measurement. The peel strength between the adhesive tape and the release sheet of this peel strength measurement sample was measured with a tensile tester (manufactured by Intesco, precision universal material tester, type 2020) in a thermostatic chamber at 25 ° C. The peeling angle was 180 degrees and the peeling speed was 300 mm / min.

(7) Blocking resistance The obtained release sheet was cut into a size of 50 mm × 50 mm, and 2 so that the surface of the resin layer 2 and the surface on which the resin layers 1 and 2 of the base material were not laminated contacted each other. The sheets are stacked and left for 24 hours under a load of 10 kPa at 60 ° C., then the load is removed and the temperature is lowered to room temperature, and the surface of the resin layer 2 and the resin layers 1 and 2 of the base material are not laminated. The blocking resistance was evaluated by examining the adhesion state with the surface. ○ (good) when the two sheets are not closely attached, or the two sheets are peeled off very lightly and the resin layer is not changed such as whitening (good), the two sheets are lightly attached, Two sheets are peeled off, a part of the resin layer is whitened △ (somewhat poor), the resin layer causes cohesive failure, or the resin layer after peeling the two sheets is totally Those that are white are marked with x (defect).

Reference example 1
(Production of acid-modified polybutadiene aqueous dispersion T-1)
60.0 g of acid-modified polybutadiene (manufactured by Evonik Degussa, polyvest OC800S, number average molecular weight 2400, acid value 70 to 90 mgKOH / g) using a stirrer equipped with a heater and a pressure-resistant 1 liter glass container , 60.0 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as IPA), 15 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as TEA) and 165 g of distilled water were charged in a glass container, When stirred at 300 rpm, the system became milky white. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 80 ° C. and further stirred for 20 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) Thus, a milky white uniform acid-modified polybutadiene aqueous dispersion T-1 was obtained.

Reference example 2
(Production of acid-modified polyisoprene aqueous dispersion T-2)
60.0 g of acid-modified polyisoprene (manufactured by Kuraray Co., Ltd., Kuraprene LIR-403, number average molecular weight 34000, acid value 9-11 mg KOH / g) using a stirrer equipped with a heater and a pressure-resistant 1 liter glass container equipped with a heater. ), 60.0 g of IPA, 15 g of TEA and 165 g of distilled water were charged into a glass container and heated while stirring at a rotation speed of 300 rpm, and the system temperature was kept at 120 ° C. for another 60 minutes. Stir. Then, after cooling to room temperature (about 25 ° C.) while stirring with air cooling, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave), milky white uniform An acid-modified polyisoprene aqueous dispersion T-2 was obtained.

Reference example 3
(Production of acid-modified polyisoprene aqueous dispersion T-3)
60.0 g of acid-modified polyisoprene (manufactured by Kuraray Co., Ltd., Kuraprene LIR-410, number average molecular weight 30000, acid value 23-30 mgKOH / g) ), 60.0 g of IPA, 15 g of TEA and 165 g of distilled water were charged into a glass container and stirred at a rotation speed of the stirring blade of 300 rpm. The system became milky white. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 120 ° C. and further stirred for 60 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky white uniform acid-modified polyisoprene aqueous dispersion T-3 was obtained.

Reference example 4
(Production of acid-modified polyolefin resin aqueous dispersion E-1)
Using a stirrer equipped with a hermetic pressure-resistant 1 liter glass container with a heater, 60.0 g of maleic anhydride-modified polyolefin resin (Arkema, Bondine LX-4110), 90.0 g of IPA, 3.0 g Of TEA and 147.0 g of distilled water were charged into a glass container. And it stirred for 30 minutes, setting the rotational speed of a stirring blade to 300 rpm, maintaining system temperature at 140-145 degreeC. Then, it put on the water bath and cooled to room temperature (about 25 degreeC), stirring with a rotational speed of 300 rpm. Furthermore, pressure filtration (air pressure 0.2 MPa) was performed with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave). As a result, a milky white uniform acid-modified polyolefin resin aqueous dispersion E-1 was obtained.

Reference Example 5
(Production of acid-modified polyolefin resin aqueous dispersion E-2)
Using “Bondyne HX-8210” (manufactured by Arkema, maleic anhydride-modified polyolefin resin) as the acid-modified polyolefin resin, the same operation as in the production of the aqueous dispersion E-1 was performed, and the acid-modified polyolefin resin aqueous dispersion Body E-2 was obtained.

  Table 1 shows the compositions and average particle diameters of the aqueous dispersions produced in Reference Examples 1 to 5.

Example 1
Acid-modified polybutadiene aqueous dispersion T-1 and an aqueous solution of an oxazoline compound (manufactured by Nippon Shokubai Co., Ltd., Epocros WS-500, solid content concentration 40% by mass, hereinafter referred to as WS-500) are added to 100 parts by mass of acid-modified polybutadiene. On the other hand, it mixed so that the quantity of solid content of an oxazoline compound might be 15 mass parts, and the liquid material 1 was obtained. This liquid material 1 was applied to a corona-treated surface of a biaxially stretched polyester resin film (manufactured by Unitika Ltd., biaxially stretched polyethylene terephthalate film, emblet S-50, thickness 50 μm, hereinafter, S-50) using a Meyer bar. After coating, the resin layer 1 having a thickness of 0.1 μm was formed on the film by drying at 150 ° C. for 15 seconds.
Furthermore, the acid-modified polyolefin resin aqueous dispersion E-1 and the aqueous solution WS-500 of the oxazoline compound are adjusted so that the solid content of the oxazoline compound is 5 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin. The liquid 2 was obtained by mixing. By applying this liquid 2 on the resin layer 1 using a Meyer bar, and then drying at 150 ° C. for 15 seconds, a resin layer 2 having a thickness of 0.1 μm is formed on the resin layer 1. A release sheet was obtained.

Example 2
In Example 1, instead of the acid-modified polyolefin resin aqueous dispersion E-1, the acid-modified polyolefin resin aqueous dispersion E-2 was used, and the amount of the oxazoline-based compound was adjusted with respect to 100 parts by mass of the acid-modified polyolefin resin. A release sheet was obtained by performing the same operation except that the amount was 1 part by mass.

Example 3
In Example 1, instead of the acid-modified polybutadiene aqueous dispersion T-1, the acid-modified polyisoprene aqueous dispersion T-2 was used, and the amount of the oxazoline compound was 5 mass with respect to 100 parts by mass of the acid-modified polyisoprene. A release sheet was obtained by carrying out the same operation except that it was part.

Example 4
In Example 2, instead of the acid-modified polybutadiene aqueous dispersion T-1, an acid-modified polyisoprene aqueous dispersion T-2 was used, and the amount of the oxazoline compound was 5 masses with respect to 100 parts by mass of the acid-modified polyisoprene. A release sheet was obtained by carrying out the same operation except that it was part.

Example 5
A release sheet was obtained in the same manner as in Example 3 except that the amount of the oxazoline compound added to the resin layer 1 was 1 part by mass with respect to 100 parts by mass of the acid-modified polyisoprene.

Example 6
In Example 3, instead of acid-modified polyisoprene aqueous dispersion T-2, acid-modified polyisoprene aqueous dispersion T-3 was used, and the amount of oxazoline compound was 15 with respect to 100 parts by mass of acid-modified polyisoprene. A release sheet was obtained by performing the same operation except that the mass part was adjusted.

Example 7
In Example 6, instead of the aqueous solution WS-500 of the oxazoline compound in the resin layer 1, an aqueous dispersion of a carbodiimide compound (Nisshinbo Co., Ltd., Carbodilite E-02, solid content concentration 40% by mass, hereinafter, E-02) Was used to obtain a release sheet, except that the amount of the carbodiimide compound was 50 parts by mass with respect to 100 parts by mass of the acid-modified polyisoprene.

Example 8
In Example 3, instead of the aqueous solution WS-500 of the oxazoline compound in the resin layer 1, an aqueous dispersion E-02 of the carbodiimide compound was used, and the amount of the carbodiimide compound relative to 100 parts by mass of the acid-modified polyisoprene. A release sheet was obtained by performing the same operation except that the amount was 20 parts by mass.

Example 9
In Example 3, instead of the aqueous solution WS-500 of the oxazoline compound in the resin layer 2, an aqueous dispersion E-02 of the carbodiimide compound was used, and the amount of the carbodiimide compound relative to 100 parts by mass of the acid-modified polyolefin resin. A release sheet was obtained by performing the same operation except that the amount was 15 parts by mass.

Example 10
In Example 3, instead of the aqueous solution WS-500 of the oxazoline compound in the resin layer 1, a melamine compound-containing solution (DIC Corporation, Becamine J-101, solid content concentration: 71% by mass, hereinafter referred to as J-101) was used. The amount of the melamine compound is 30 parts by mass with respect to 100 parts by mass of the acid-modified polyisoprene. Further, instead of the oxazoline compound aqueous solution WS-500 of the resin layer 2, a melamine compound-containing solution J-101 is used. A release sheet was obtained by performing the same operation except that the amount of the melamine compound was 50 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin.

Example 11
A release sheet was obtained in the same manner as in Example 3 except that the thickness of the resin layer 1 was changed to 0.01 μm.

Example 12
A release sheet was obtained in the same manner as in Example 3 except that the thickness of the resin layer 2 was 0.3 μm.

Example 13
A release sheet was obtained in the same manner as in Example 3 except that the thickness of the resin layer 2 was set to 0.05 μm.

Example 14
A release sheet was obtained in the same manner as in Example 3 except that the thickness of the resin layer 2 was 0.2 μm.

Example 15
A release sheet was obtained in the same manner as in Example 11 except that the thickness of the resin layer 2 was set to 0.01 μm.

Example 16
A release sheet was obtained in the same manner as in Example 3 except that the thickness of the resin layer 1 was 0.3 μm and the thickness of the resin layer 2 was 0.3 μm.

Comparative Example 1
In Example 1, the same operation was performed except that the resin layer 2 was not laminated, so that a release sheet composed of the base material and the resin layer 1 was obtained.

Comparative Example 2
In Example 3, the same operation was performed except that the resin layer 2 was not laminated to obtain a release sheet composed of the base material and the resin layer 1.

Comparative Example 3
In Example 1, the same operation was performed except that the resin layer 1 was not laminated, so that a release sheet composed of the base material and the resin layer 2 was obtained.

Comparative Example 4
A release sheet was obtained in the same manner as in Example 1 except that the resin layer 1 was formed without using the oxazoline compound.

Comparative Example 5
A release sheet was obtained in the same manner as in Example 1 except that the resin layer 2 was formed without using the oxazoline compound.

Comparative Example 6
In Example 3, a release sheet was obtained by performing the same operation except that the addition amount of the oxazoline compound in the resin layer 1 was 60 parts by mass with respect to 100 parts by mass of the acid-modified polyisoprene. .

Comparative Example 7
In Example 3, a release sheet was obtained by performing the same operation except that the addition amount of the oxazoline compound in the resin layer 2 was 60 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin. .

Comparative Example 8
A release sheet was obtained in the same manner as in Example 3 except that the thickness of the resin layer 2 was changed to 0.4 μm.

Comparative Example 9
In Example 3, a release sheet was obtained by performing the same operation except that the thickness of the resin layer 1 was 0.4 μm.

  Table 2 shows the structures of the resin layers 1 and 2, the measurement results of the peel strength, and the evaluation results of the blocking resistance for the release sheets obtained in Examples and Comparative Examples.

  A resin layer 1 having a thickness of 0.01 to 0.3 μm containing 1 to 50 parts by mass of a crosslinking agent is provided for 100 parts by mass of the acid-modified polybutadiene or acid-modified polyisoprene obtained in Examples 1 to 16. Furthermore, the release sheet obtained by laminating the resin layer 2 having a thickness of 0.01 to 0.3 μm containing 1 to 50 parts by mass of the crosslinking agent with respect to 100 parts by mass of the acid-modified polyolefin resin has a release property and resistance It was excellent in blocking.

On the other hand, as shown in Comparative Examples 1 and 2, when the resin layer constituting the release sheet is only the resin layer 1 containing acid-modified polybutadiene or acid-modified polyisoprene and a crosslinking agent, the release property is good. Although there was, blocking resistance was inadequate. As shown in Comparative Example 3, when the resin layer constituting the release sheet is only the resin layer 2 containing the acid-modified polyolefin resin and the crosslinking agent, the blocking resistance is sufficient but the release property is insufficient. It was something.
As shown in Comparative Example 4, when the resin layer 1 did not contain a cross-linking agent, the releasability and blocking resistance were insufficient. When the resin layer 2 did not contain a crosslinking agent as shown in Comparative Example 5, the heat resistance was inferior, and the releasability was lowered after high temperature storage.
As shown in Comparative Examples 6 and 7, when the amount of the crosslinking agent exceeded the range specified in the present invention, the releasability was insufficient.
As shown in Comparative Example 8, when the thickness of the resin layer 2 exceeded the range specified in the present invention, the releasability was insufficient. As shown in Comparative Example 9, when the thickness of the resin layer 1 exceeded the range defined in the present invention, the blocking resistance was insufficient.

Claims (5)

  A release sheet in which a resin layer 1 and a resin layer 2 are laminated in this order on a substrate, the resin layer 1 comprising 100 parts by mass of acid-modified polybutadiene and / or acid-modified polyisoprene, an oxazoline compound, and carbodiimide 1 to 50 parts by mass of a crosslinking agent containing at least one selected from a compound and a melamine compound, the thickness of the resin layer 1 is 0.01 to 0.3 μm, and the resin layer 2 is an acid-modified polyolefin resin 100 masses And 1 to 50 parts by mass of a crosslinking agent containing at least one selected from an oxazoline compound, a carbodiimide compound, and a melamine compound, and the thickness of the resin layer 2 is 0.01 to 0.3 μm, Release sheet.   The release sheet according to claim 1, wherein the peel strength between the resin layer 2 and the acrylic adhesive material is 0.5 N / cm or less.   The release sheet according to claim 1 or 2, wherein the substrate is any one of a resin material, paper, synthetic paper, cloth, metal material, and glass material.   The release sheet according to claim 3, wherein the resin material is a polyester resin film. A method for producing a release sheet according to claim 1, comprising 100 parts by mass of acid-modified polybutadiene and / or acid-modified polyisoprene and at least one selected from oxazoline compounds, carbodiimide compounds, and melamine compounds. The liquid 1 dispersed in an aqueous medium containing 1 to 50 parts by mass of the agent is applied on the substrate and then dried to form the resin layer 1, and then 100 parts by mass of the acid-modified polyolefin resin and the oxazoline compound The liquid material 2 dispersed in an aqueous medium containing 1 to 50 parts by mass of a crosslinking agent containing at least one selected from carbodiimide compounds and melamine compounds is applied onto the resin layer 1 and then dried to obtain a resin layer 2. Forming a release sheet.