WO2014010733A1

WO2014010733A1 - Photoreactant-layer-containing sheet and method for manufacturing photoreactant-layer-containing sheet

Info

Publication number: WO2014010733A1
Application number: PCT/JP2013/069190
Authority: WO
Inventors: 悠司豊田; 平松　剛
Original assignee: 日東電工株式会社
Priority date: 2012-07-13
Filing date: 2013-07-12
Publication date: 2014-01-16
Also published as: JP2014031005A

Abstract

A photoreactant-layer-containing sheet comprising a light-transmitting film, said light-transmitting film having been released-treated by a non-silicone release agent, bonded to at least one surface of a photoreactant layer obtained by photoreacting a photoreactive composition. The peel force of the light-transmitting film relative to the photoreactant layer is less than or equal to 1.0 N/25 mm.

Description

Photoreactant layer-containing sheet and method for producing photoreactor layer-containing sheet

The present invention relates to a method for producing a photoreactive material layer-containing sheet, in which a light-transmitting film that has been subjected to a release treatment with a release agent is bonded to at least one surface of a photoreactive material layer, and a laminated sheet produced by the method. .

For example, a sheet containing a photoreactant layer obtained by photoreacting a photoreactive composition, such as an adhesive sheet having an adhesive layer made of an acrylic polymer-based adhesive obtained by polymerization by light irradiation, that is, a photoreactant The layer-containing sheet has not only excellent weather resistance, heat resistance, and chemical resistance, but also has an advantage that it can be produced without using an organic solvent that causes air pollution, which has recently become a problem.

However, for example, the photopolymerization reaction by light irradiation has a problem of polymerization inhibition due to oxygen, and in order to prevent this polymerization inhibition, a method of performing a photopolymerization reaction under a nitrogen atmosphere has been conventionally known (Patent Document). 1). However, in such a method, the monomer is volatilized from the photoreactive composition (photopolymerizable composition), and the monomer composition in the polymer that is the resulting photoreactive substance is changed, or the light irradiation lamp is changed depending on the volatilized monomer. There has been a problem of being contaminated, and there has been a problem that the equipment cost of the light irradiation zone becomes expensive when trying to avoid such contamination.

As another method, as in Patent Document 2, the light-reactive composition layer is covered with a light-transmitting film so that the light-reactive composition layer is shielded from oxygen, and then light-reactive through the light-transmitting film. A method of irradiating the composition layer with light is known. Further, the photoreactive composition layer is a photoreactive composition layer comprising a photoreactive composition in which the reaction product after light irradiation exhibits adhesiveness, such as a photopolymerizable composition for an adhesive layer. In some cases, the light-transmitting film for shielding from oxygen is applied to the surface of the base material (film) so that good peelability can be obtained from the photoreactive composition layer after light irradiation (after polymerization reaction). The thing which apply | coated the silicone type release agent is known. This is because the silicone release agent is extremely light release, and it is difficult to cause heavy release even for a reaction product (polymer) that exhibits adhesiveness after light irradiation (after polymerization reaction).

JP 2002-138258 A JP 2004-322408 A

However, in the case of a photoreactive material layer-containing sheet obtained by using a light-transmitting film that has been release-treated with a silicone-based release agent, the silicone component is transferred from the release agent layer of the light-transmitting film to the photoreactive composition layer. Therefore, when the photoreactant layer-containing sheet obtained after the photoreaction is used for electronic devices such as HDDs or for automobiles, the silicone component mixed in the photoreactant layer may cause defects in electronic devices or automobiles. There is a problem that the silicone release agent cannot be applied to the photoreactive material layer-containing sheet for these uses.

This invention is made | formed in view of such a situation, and can peel a light transmissive film from a photoreaction material layer, without using a silicone type release agent for the mold release process of a light transmissive film. It aims at providing a photoreaction material layer containing sheet.

As a result of intensive studies by the present inventors, a light-transmitting film which has been subjected to a release treatment with a specific release agent mainly composed of polyolefin, which is a non-silicone release agent, is in contact with the photoreactive composition layer. By knowing that even if a photoreaction of the photoreactive composition layer is carried out in this state, the photoreactive material layer obtained after the photoreaction does not delaminate, and further research based on this knowledge The present invention has been completed.

The present invention is as follows.
[1] A photoreactive material layer-containing sheet in which a light transmissive film subjected to a release treatment with a non-silicone release agent is bonded to at least one surface of a photoreactive material layer obtained by photoreaction of a photoreactive composition. And
A photoreactive material layer-containing sheet, wherein a peel strength of the light transmissive film with respect to the photoreactive material layer is 1.0 N / 25 mm or less.
[2] The photoreactive material layer-containing sheet according to the above [1], wherein the silicone component adhesion amount on the surface of the photoreactive material layer on which the light transmissive film is bonded is less than 1.0 [kcps].
[3] The photoreactant layer-containing sheet according to the above [1] or [2], wherein the non-silicone release agent is a polyolefin release agent containing at least polyolefin, isocyanate and polyolefin polyol.
[4] The photoreactive material layer-containing sheet according to the above [3], wherein the polyolefin release agent further contains a urethanization catalyst.
[5] The photoreactant layer-containing sheet according to the above [4], wherein the urethanization catalyst is a metal complex catalyst or / and an organotin catalyst.
[6] Polyolefin content in the release agent is 80% by mass or more, 90% by mass or more of the polyolefin is a polyolefin having a tensile elastic modulus at 23 ° C. of 10 MPa or less and a tensile fracture stress at 23 ° C. of 15 MPa or less. The photoreactive material layer-containing sheet according to any one of the above [3] to [5].
[7] The photoreactive material layer-containing sheet according to the above [6], wherein the photoreactive composition is a photopolymerizable composition for pressure-sensitive adhesives, and the photoreactive material layer is a pressure-sensitive adhesive layer.
[8] A monomer mixture in which the photopolymerizable composition for an adhesive contains an alkyl acrylate monomer as a main component monomer and a polar group-containing monomer copolymerizable with the alkyl acrylate monomer The photoreactant layer-containing sheet according to the above [7], which is a photopolymerizable composition for an acrylic pressure-sensitive adhesive containing a photopolymerization initiator.
[9] The above-mentioned monomer mixture is composed of 70 to 100% by mass of an alkyl acrylate monomer having an alkyl group having 1 to 18 carbon atoms and 30 to 0% by mass of a polar group-containing monomer. The photoreactive material layer-containing sheet according to [8].
[10] The polyolefin content in the release agent is 80% by mass or more, 90% by mass or more of the polyolefin is a polyolefin having a tensile elastic modulus at 23 ° C. of 25 MPa or more and a tensile fracture stress at 23 ° C. of 8 MPa or more. The photoreactive material layer-containing sheet according to any one of the above [3] to [5].
[11] The photoreactive material layer-containing sheet according to the above [10], wherein the photoreactive composition is a photopolymerizable composition for an acrylic urethane substrate, and the photoreactive material layer is an acrylic urethane substrate.
[12] The photopolymerizable composition for an acrylic urethane base material is a composition containing a radical polymerizable monomer whose main component monomer is an alkyl acrylate monomer, a urethane polymer, and a photopolymerization initiator. The photoreactive material layer-containing sheet according to the above [11].
[13] The photoreactive material layer-containing sheet according to any one of [1] to [12], wherein the light transmissive film is a polyester film.
[14] A release agent layer of a light-transmitting film in which a photoreactive composition layer is formed on at least one side of a support, and a release treatment is performed on the outer surface of the photoreactive composition layer with a non-silicone release agent. Or a photoreactive composition layer was formed on a release agent layer of a light-transmitting film which was release-treated with a non-silicone release agent, and a support was laminated on the photoreactive composition layer. Thereafter, by irradiating with light, a photoreactive material layer is formed by photoreacting the photoreactive composition layer, and a method for producing a photoreactive material layer-containing sheet,
The method for producing a photoreactant layer-containing sheet, wherein the non-silicone release agent is a polyolefin release agent containing at least polyolefin, isocyanate and polyolefin polyol.
[15] The method according to [14] above, wherein the polyolefin release agent further contains a urethanization catalyst.
[16] The method according to [15] above, wherein the urethanization catalyst is a metal complex catalyst or / and an organotin catalyst.
[17] The method according to any one of [14] to [16] above, wherein the photoreactive composition is a photopolymerizable composition for pressure-sensitive adhesives, and the photoreactive material layer is a pressure-sensitive adhesive layer.
[18] Polyolefin in which the polyolefin content in the polyolefin release agent is 80% by mass or more, 90% by mass or more of the polyolefin has a tensile elastic modulus at 23 ° C. of 10 MPa or less, and a tensile fracture stress at 23 ° C. of 15 MPa or less. The method according to [17] above, wherein
[19] A monomer in which the photopolymerizable composition for pressure-sensitive adhesives contains an alkyl acrylate monomer as a main component monomer and a polar group-containing monomer copolymerizable with the alkyl acrylate monomer. The method according to [17] or [18] above, wherein the mixture contains a photopolymerization initiator.
[20] The above-mentioned monomer mixture is composed of 70 to 100% by mass of an alkyl acrylate monomer having an alkyl group having 1 to 18 carbon atoms and 30 to 0% by mass of a polar group-containing monomer. [19] The method described.
[21] The method according to any one of [14] to [16] above, wherein the photoreactive composition is a photopolymerizable composition for an acrylic urethane substrate, and the photoreactive material layer is an acrylic urethane substrate.
[22] The photopolymerizable composition for an acrylic urethane base material is a composition containing a radical polymerizable monomer whose main component monomer is an alkyl acrylate monomer, a urethane polymer, and a photopolymerization initiator. The method according to [21] above.
[23] A polyolefin having a polyolefin release agent content of 80% by mass or more, 90% by mass or more of the polyolefin having a tensile elastic modulus at 23 ° C. of 10 MPa or less, and a tensile fracture stress at 23 ° C. of 15 MPa or less. The method according to [22] above, wherein
[24] A photoreactive material layer-containing sheet produced by the method according to any one of [14] to [23].

According to the present invention, since the non-silicone release agent is used for the release treatment of the light transmissive film, there is no problem of migration of the silicone component to the photoreactive composition layer, and the non-silicone release agent is used. However, it is possible to realize a photoreactive material layer-containing sheet in which the light transmissive film can be easily peeled from the photoreactive composition layer after photoreaction (that is, the photoreactive material layer). For this reason, for example, when the photoreactive material layer-containing sheet is a pressure-sensitive adhesive sheet or pressure-sensitive adhesive tape containing a pressure-sensitive adhesive layer as the photoreactive material layer, it can be suitably used for electronic equipment applications and automotive applications.

Hereinafter, the present invention will be described in detail according to the embodiment.
In the photoreactive material layer-containing sheet of the present invention, a light-transmitting film subjected to a release treatment with a non-silicone release agent is bonded to at least one surface of a photoreactive material layer obtained by photoreacting a photoreactive composition. The main feature is that the peel strength of the light-transmitting film with respect to the photoreactive material layer is 1.0 N / 25 mm or less.

The shape of the photoreactive material layer-containing sheet of the present invention is a concept including not only “sheet shape” but also shapes generally called “tape shape”, “film shape” and the like.

In this specification, the expression “(meth) acrylic acid” means both “acrylic acid” and “methacrylic acid”, and “(meth) acrylate” means both “acrylate” and “methacrylate”. Means. The “photoreaction” is typically a “photopolymerization reaction”.

1. Light transmissive film

The light-transmitting film used in the present invention is a light-transmitting film in which at least the surface in contact with the photoreactive composition layer is release-treated with a non-silicone release agent, and the light-transmitting base film, It has at least a release agent layer formed on at least one surface of the base film. In the present specification, the photoreactive composition layer is a photoreactive material layer, and the “surface of the light transmissive film in contact with the photoreactive composition layer” results in “light transmissive property”. It is the surface that contacts the photoreactive material layer of the film.

[Release layer]

The release agent is a non-silicone release agent, and the release force of the light transmissive film to the photoreactive composition layer after photoreaction (that is, the photoreactive material layer) is 1.0 N / 25 mm or less. If it is an agent, it can be used without restriction, but among them, a polyolefin-based release agent containing polyolefin, isocyanate and polyolefin polyol as essential components is preferable.

[Polyolefin release agent]

(Polyolefin)
The polyolefin release agent contains one or more polyolefins. In the present invention, “polyolefin” means a polyolefin that is solid at 38 ° C.

Any polyolefin can be used as long as it can be dissolved in an organic solvent together with other components and applied to the base film.

From the viewpoint of solubility in an organic solvent, the density of the polyolefin is preferably 0.885 g / cm ³ or less, more preferably 0.880 g / cm ³ or less. When this density exceeds 0.885 g / cm ³ , the solubility in an organic solvent is lowered, and application to a substrate film tends to be difficult, and the peeling force tends to increase. On the other hand, the lower limit of the density of the polyolefin is not particularly limited, but this density is preferably 0.830 g / cm ³ or more, more preferably 0.857 g / cm ³ or more, and further preferably 0.858 g / cm ³ or more. is there.

Examples of the polyolefin include an α-olefin copolymer formed from at least two monomers selected from the group consisting of ethylene, propylene and an α-olefin having 4 to 20 carbon atoms. Among these, a copolymer having ethylene as a main monomer (that is, an ethylene-based α-olefin copolymer) and / or a copolymer having propylene as a main monomer (that is, a propylene-based α-olefin). Copolymer) is preferred. Here, as the α-olefin having 4 to 20 carbon atoms, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1- Examples include pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene and the like. The α-olefin copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer.

The density of the ethylene-based α-olefin copolymer is preferably 0.857 g / cm ³ or more and 0.885 g / cm ³ or less (more preferably 0.880 g / cm ³ or less). The ethylene structural unit amount of the ethylene-based α-olefin copolymer is 50 mol% or more, preferably 60 to 95 mol%, more preferably 70 to 95 mol%. The α-olefin structural unit contained in the ethylene-based α-olefin copolymer is one formed from at least one monomer selected from the group consisting of 1-butene, propylene, 1-hexene and 1-octene. preferable. Particularly preferred ethylene-based α-olefin copolymers include ethylene-1-butene copolymers and ethylene-propylene copolymers. Such an ethylene-1-butene copolymer may contain a structural unit derived from α-olefin other than ethylene and 1-butene in an amount of 10 mol% or less. Similarly, the ethylene-propylene copolymer may contain a structural unit derived from an α-olefin other than ethylene and propylene in an amount of 10 mol% or less. Such a copolymer is produced, for example, by copolymerizing ethylene and α-olefin using a catalyst comprising a transition metal catalyst component (for example, vanadium compound or zirconium compound) and an organoaluminum compound catalyst component. be able to.

The density of the propylene-based α-olefin copolymer is preferably 0.858 g / cm ³ or more and 0.885 g / cm ³ or less (more preferably 0.880 g / cm ³ or less). The propylene structural unit amount of the propylene-based α-olefin copolymer is more than 50 mol%. The propylene structural unit amount is preferably 60 to 95 mol%, more preferably 70 to 95 mol%. The α-olefin structural unit contained in the propylene-based α-olefin copolymer is formed of at least one monomer selected from the group consisting of ethylene, 1-butene, 1-hexene and 1-octene. Those are preferred. A particularly preferred propylene-based α-olefin copolymer is a propylene-ethylene random copolymer (propylene-based elastomer). The propylene-ethylene random copolymer may contain a constituent unit derived from α-olefin other than propylene and ethylene in an amount of 10 mol% or less. The propylene-based α-olefin copolymer can be produced using a metallocene catalyst as described in, for example, JP-A No. 2000-191862.

Commercially available products can be used as the α-olefin copolymer. Preferable commercial products of the ethylene-based α-olefin copolymer include, for example, Tuffmer P series, Tuffmer A series (all manufactured by Mitsui Chemicals), Engage (manufactured by Dow Chemical Company), and the like. In addition, as a preferable commercial product of the propylene-based α-olefin copolymer, for example, Tuffmer XM series (manufactured by Mitsui Chemicals) and the like can be mentioned.

Polymethylpentene can also be used as the polyolefin. Examples of polymethylpentene include homopolymers of 4-methyl-1-pentene, and copolymers of 4-methyl-1-pentene and other α-olefins (that is, 4-methyl-1-pentene α-olefins). Olefin copolymer). The amount of 4-methyl-1-pentene constituent unit in the polymethylpentene copolymer is preferably 50 to 95 mol%, more preferably 70 to 95 mol%. The polymethylpentene may be a crystalline polymer. The density of polymethylpentene is preferably 0.083 to 0.869 / cm ³ . Examples of the α-olefin structural unit in the polymethylpentene copolymer include 2 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like. Those derived from .alpha.-olefins of .about.20 are preferred. Among these, 1-decene, 1-tetradecene and 1-octadecene, which show good copolymerizability with 4-methyl-1-pentene, are more preferable. An example of a commercially available product of polymethylpentene is TPX-S (4-methyl-1-pentene α-olefin copolymer, manufactured by Mitsui Chemicals).

The polyolefin preferably does not react with the isocyanate described below. However, a modified polyolefin having a functional group such as a hydroxyl group (hydroxy group), an amino group, a carboxy group, or an isocyanate group (isocyanato group) may be used as long as the object of the present invention is not impaired. The number of functional groups (average value) per molecule of the modified polyolefin is preferably 1 or less.

When only one type of polyolefin is used as the release agent, the MFR (melt flow rate) at 230 ° C. of the polyolefin is preferably 100 g / 10 minutes from the viewpoint of the strength (coating strength) of the release agent layer to be formed. Hereinafter, it is more preferably 70 g / 10 min or less, further preferably 50 g / 10 min or less, particularly preferably 10 g / 10 min or less. On the other hand, when two or more polyolefins are used as the release agent, the MFR at 230 ° C. of at least one of the polyolefins is preferably 100 g / 10 min or less, more preferably 70 g / 10 min or less, and even more preferably 50 g / It is 10 minutes or less, particularly preferably 10 g / 10 minutes or less. The content of the polyolefin having such MFR is preferably 10% by mass or more, more preferably 50% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass in the total polyolefin.

In the present invention, the photoreactive composition is a photoreaction in which a product obtained by photoreacting it, such as a photopolymerizable composition for an adhesive such as an acrylic adhesive, exhibits tack at 23 ° C. In the case of an adhesive composition (hereinafter also referred to as “tack-expressing photoreactive composition”), the polyolefin used for the polyolefin-based release agent may be an ethylene-based α-olefin copolymer and / or a propylene-based α-olefin copolymer. The use of coalescence is preferable from the viewpoint of preventing the peel force from increasing with time.

In addition, when the photoreactive composition is a tack development type photoreactive composition, the photoreactive composition layer after the photoreaction, that is, the dependency of the light-transmitting film on the photoreactive substance layer and the peeling speed dependency In order to reduce the polyolefin, a polyolefin (A-1) having a tensile modulus at 23 ° C. of 10 MPa or less and a tensile fracture stress at 23 ° C. of 15 MPa or less is 90% by mass or more in the total polyolefin. It is preferable to contain by quantity. In other words, the content of the polyolefin (A-2) other than the polyolefin (A-1) is preferably limited to 10% by mass or less in the total polyolefin. In addition, the peeling rate dependence here means that the peeling force of the light-transmitting film with respect to the photoreactive material layer depends on the peeling rate, and more specifically, the high-speed peeling compared with the peeling force at the low-speed peeling. This means that the peel strength at is large.

Any of the above-described polyolefin (A-1) and polyolefin (A-2) may be used alone or in combination of two or more. The content of the polyolefin (A-1) is more preferably 95% by mass or more, further preferably 100% by mass in the total polyolefin.

The use of polyolefin (A-1) reduces the release rate dependency because the tensile fracture stress is assumed under the assumption that in the peeling process, fracture occurs near the interface between the photoreactant layer and the release agent layer. Since the presence of polyolefin (A-1) having a small size destroys the vicinity of the interface with a small force, it is estimated that an increase in the peeling force can be suppressed even if the peeling speed is increased. It is not something.

The tensile modulus at 23 ° C. of the polyolefin (A-1) is 10 MPa or less, preferably 8 MPa or less, more preferably 7 MPa or less, and even more preferably 6 MPa or less. The tensile fracture stress of the polyolefin (A-1) at 23 ° C. Is 15 MPa or less, preferably 8 MPa or less, more preferably 6 MPa or less, and particularly preferably 4 MPa or less. Polyolefin (A-2) having a tensile modulus of elasticity exceeding 10 MPa at 23 ° C. tends to increase the peel strength of the light-transmitting film when peeled at a low speed and a high speed, and the tensile fracture stress at 23 ° C. exceeds 15 MPa. Polyolefin (A-2) tends to increase the peel strength of the light transmissive film when peeled at high speed.

As the polyolefin (A-2), (i) a polyolefin having a tensile fracture stress at 23 ° C. of 15 MPa or less and a tensile modulus at 23 ° C. of more than 10 MPa; (ii) a tensile modulus at 23 ° C. of 10 MPa or less And (iii) a polyolefin having a tensile modulus at 23 ° C. of greater than 10 MPa and a tensile fracture stress at 23 ° C. of greater than 15 MPa. Among these, the polyolefin (A-2) of the embodiment (ii) is preferable. The tensile modulus at 23 ° C. of the polyolefin (A-2) is preferably 100 MPa or less, and the tensile fracture stress at 23 ° C. of the polyolefin (A-2) is preferably 35 MPa or less.

There is no limitation on either the tensile modulus of elasticity of the polyolefin (A-1) at 23 ° C. or the lower limit of the tensile fracture stress at 23 ° C. However, in order to obtain sufficient release agent layer strength (coating film strength), the tensile modulus of elasticity of the polyolefin (A-1) at 23 ° C. is preferably 2 MPa or more, more preferably 3 MPa or more. The fracture stress is preferably 1 MPa or more, more preferably 2 MPa or more.

As the polyolefin (A-1), commercially available products can be used. For example, Tuffmer A-0550S, Tuffmer A-1050S, Tuffmer A-4050S, Tuffmer A-4070S, Tuffmer A-1070S, Tuffmer P-0080K, Tuffmer P-0280 Tuffmer A-3570S, Tuffmer P-0680, Tuffmer P-0180, Tuffmer P-0480, Tuffmer P-0275, Tuffmer P-0775 (all of which are ethylene-based α-olefin copolymers, manufactured by Mitsui Chemicals, Inc.) Can be mentioned.

As the polyolefin (A-2), commercially available products can be used. For example, Tafmer XM-7070 (propylene-based α-olefin copolymer, Mitsui Chemicals), TPX-S (4-methyl-1-pentene-based α-olefin) Copolymer, manufactured by Mitsui Chemicals, Inc.).

In the present invention, the photoreactive composition is a photoreactive composition (such as a photopolymerizable composition for an acrylic urethane substrate) in which a product obtained by photoreacting it does not exhibit tack at 23 ° C. ( (Hereinafter also referred to as “tack non-expression type photoreactive composition”), the photoreactive composition layer after the photoreaction, that is, the peeling force of the light transmissive film with respect to the photoreactive substance layer is reduced and peeled off. In order to increase the speed dependency, the polyolefin used for the polyolefin release agent is a polyolefin (A-3) having a tensile modulus at 23 ° C. of 25 MPa or more and a tensile fracture stress at 23 ° C. of 8 MPa or more. The aspect which contains in the quantity of 90 mass% or more in this is preferable. In other words, the content of the polyolefin (A-4) other than the polyolefin (A-3) is preferably limited to 10% by mass or less in the total polyolefin. Here, the peeling speed dependency means that the peeling force of the light-transmitting film depends on the peeling speed. More specifically, the peeling force at high speed peeling is higher than the peeling power at low speed peeling. It is small.

Any of the above-mentioned polyolefin (A-3) and polyolefin (A-4) may be used alone or in combination of two or more. The content of the polyolefin (A-3) is more preferably 95% by mass or more, and still more preferably 100% by mass in the total polyolefin.

As the polyolefin (A-3), a commercially available product can be used. For example, TAFMER XM-7070 (propylene-based α-olefin copolymer, manufactured by Mitsui Chemicals), TPX-S (4-methyl-1-pentene-based α-olefin) Copolymer, manufactured by Mitsui Chemicals, Inc.).

The use of the polyolefin (A-3) can increase the release rate dependency because the tensile elasticity is assumed under the assumption that in the peeling process, fracture occurs near the interface between the photoreactant layer and the release agent layer. It is presumed that the presence of the polyolefin (A-3) having a large rate makes it an elastic body by increasing the peeling speed and reducing the peeling force, but is not limited to such estimation. .

The tensile modulus of elasticity of the polyolefin (A-3) at 23 ° C. is 25 MPa or more, preferably 30 MPa or more, more preferably 35 MPa or more, and further preferably 40 MPa or more. The tensile fracture stress of the polyolefin (A-4) at 23 ° C. Is 8 MPa or more, preferably 12 MPa or more, more preferably 15 MPa or more. The upper limit of the tensile modulus at 23 ° C. and the tensile fracture stress at 23 ° C. of the polyolefin (A-3) is not particularly limited, but the tensile modulus at 23 ° C. is preferably 100 MPa or less, and the tensile fracture at 23 ° C. The stress is preferably 35 MPa or less. Polyolefin (A-4) having a tensile modulus at 23 ° C. of less than 25 MPa and polyolefin (A-4) having a tensile fracture stress of less than 8 MPa at 23 ° C. increase the release force of the release agent layer when peeled at high speed. There is a tendency to make it.

As the polyolefin (A-4), (i) a polyolefin having a tensile fracture stress at 23 ° C. of 8 MPa or more and a tensile elastic modulus at 23 ° C. of less than 25 MPa; (ii) a tensile elastic modulus at 23 ° C. of 25 MPa or more. And (iii) a polyolefin having a tensile modulus at 23 ° C. of less than 25 MPa and a tensile fracture stress at 23 ° C. of less than 8 MPa. The tensile modulus of elasticity of the polyolefin (A-4) at 23 ° C. is preferably 10 MPa or more, and the tensile fracture stress of the polyolefin (A-4) at 23 ° C. is preferably 2 Pa or more.

As the polyolefin (A-4), commercially available products can be used, such as Tuffmer A-0550S, Tuffmer A-1050S, Tuffmer A-4050S, Tuffmer A-4070S, Tuffmer A-1070S, Tuffmer P-0080K, Tuffmer P- 0280, Tuffmer A-3570S, Tuffmer P-0680, Tuffmer P-0180, Tuffmer P-0480, Tuffmer P-0275, Tuffmer P-0775 (all of which are ethylene-based α-olefin copolymers, manufactured by Mitsui Chemicals, Inc.) Can be mentioned.

In the present invention, the “tensile modulus at 23 ° C.” and “tensile fracture stress at 23 ° C.” of the polyolefin are values measured by the following methods. Polyolefin is dissolved in toluene to make a 5 to 10% by weight solution, and this is applied onto a release film made of polyethylene terephthalate (PET) using a baker type applicator or a doctor blade type applicator, and then heated with a hot air dryer. Heat-dry (100 ° C., 3 minutes), and immediately after the heat-dry, cool in a 23 ° C. atmosphere to produce a polyolefin film having a thickness of 20 μm after drying. If the solubility in toluene is poor, it may be dissolved by heating as necessary. The obtained polyolefin film was cut into strips of 30 mm length x 100 mm width, and while peeling off the polyolefin film from the release film, it was tightly wound in the longitudinal direction around one short side of the cut film as a length. A 30 mm rod-shaped sample is used. This rod-shaped sample was subjected to a tensile test with a tensile tester (manufactured by Shimadzu Corp., Autograph AG-IS type) under an atmosphere of 23 ° C. under conditions of a distance between chucks of 10 mm and a tensile speed of 50 mm / min. Obtain the stress-strain curve. The tensile modulus is calculated from the slope of the stress-strain curve immediately after the start of tension. Further, the stress when the rod-shaped sample is broken is determined as the tensile fracture stress.

The polyolefin content in the polyolefin release agent is usually 80% by mass or more, preferably 80 to 99% by mass, more preferably 90 to 98% by mass. When this content is less than 80% by mass, the peeling force tends to increase. On the other hand, when it exceeds 99% by mass, there are too few crosslinking components, and it is difficult to obtain sufficient release agent layer strength. In addition, the amount of the organic solvent is not included in the “release agent” serving as a reference for the content.

(Isocyanate)
The polyolefin release agent contains one or more isocyanates. Isocyanates include aromatic and aliphatic isocyanates. The aliphatic isocyanate may be a chain aliphatic isocyanate or an alicyclic isocyanate. Among these, aromatic isocyanate and alicyclic isocyanate are preferable. Since aromatic isocyanate and alicyclic isocyanate have low compatibility with polyolefin, even if they are used, the releasability of the release agent layer is not impaired. Moreover, the aromatic isocyanate and alicyclic isocyanate with low compatibility with polyolefin are unevenly distributed between the formed release agent layer and the light-transmitting film, and greatly contribute to the improvement of the adhesion between them.

In order to form a release agent layer having excellent adhesion to a base film and heat resistance, the isocyanate is preferably a polyisocyanate having three or more isocyanate groups in one molecule. The polyisocyanate is preferably at least one selected from the group consisting of an aromatic polyisocyanate and an alicyclic polyisocyanate, more preferably a group consisting of a polyhydric alcohol adduct of an aromatic diisocyanate and a polyhydric alcohol adduct of an alicyclic diisocyanate. Is at least one selected from

Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and the like. Of these, tolylene diisocyanate and xylylene diisocyanate are preferred.

Examples of the alicyclic diisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, trans-cyclohexane diisocyanate, hydrogenated tolylene diisocyanate, and the like. Of these, isophorone diisocyanate and hydrogenated xylylene diisocyanate are preferred.

Examples of the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol. Of these, trimethylolpropane is preferred.

The polyhydric alcohol adduct of aromatic diisocyanate is obtained by reacting polyhydric alcohol with an excess of aromatic diisocyanate, and the polyhydric alcohol adduct of alicyclic diisocyanate is obtained with a large amount of excess of aromatic diisocyanate. It is obtained by reacting a monohydric alcohol. The polyhydric alcohol adduct of aromatic diisocyanate is preferably a polyhydric alcohol adduct of tolylene diisocyanate or xylylene diisocyanate, more preferably a polyhydric alcohol adduct of tolylene diisocyanate. The polyhydric alcohol adduct of tolylene diisocyanate has excellent reactivity and can achieve excellent adhesion to a base film. The polyhydric alcohol adduct of alicyclic diisocyanate is preferably a polyhydric alcohol adduct of hydrogenated xylylene diisocyanate or isophorone diisocyanate.

An aromatic diisocyanate or an alicyclic diisocyanate multimer (for example, an isocyanurate) can also be suitably used as the polyisocyanate in the present invention.

In the present invention, the content of isocyanate in the release agent is preferably 0.5 to 20 parts by mass, more preferably 1.0 to 15 parts by mass, and still more preferably 1. 5 to 10 parts by mass. If isocyanate is used in such a content, there is no adverse effect such as shortening the pot life of the release agent, and more excellent adhesion to the substrate film can be obtained.

(Polyolefin polyol)

The polyolefin-based release agent contains one or more polyolefin polyols. Polyolefin polyol is used to react with isocyanate in the formation of the release agent layer. As the polyolefin polyol, those having good compatibility with the polyolefin are preferable.

The number average molecular weight (Mn) of the polyolefin polyol is preferably 1500 to 50000, more preferably 1500 to 4000, and still more preferably 1500 to 3000. A polyolefin polyol having Mn in such a range has moderate solubility in both polyolefin and isocyanate. Therefore, such a polyolefin polyol can improve the release agent layer strength and heat resistance, while not impairing the appearance of the release agent layer. In addition, when this Mn is outside the above range, a release agent layer having a whitish and cloudy appearance may be obtained. Furthermore, if this Mn is within the above range, the hydroxyl group resulting from the polyolefin polyol does not become excessive in the portion where the isocyanate on the side opposite to the base film side of the release agent layer is not unevenly distributed, and the peeling is low. An agent layer is obtained. Furthermore, if this Mn is within the above range, the isocyanate and polyolefin polyol can react appropriately in the portion where the isocyanate on the base film side of the release agent layer is unevenly distributed, and more excellent to the base film. Adhesion can be obtained.

In the present invention, the type of polyolefin polyol is not particularly limited. Examples of polyolefin polyols include polyethylene polyols, polypropylene polyols, hydrogenated polyisoprene polyols, and hydrogenated polybutadiene polyols. Among these, polyethylene polyols are preferable from the viewpoint of compatibility with polyolefins and influence on peeling force.

In addition, the hydroxyl value (mgKOH / g) of the polyolefin polyol is preferably 20 or more from the viewpoint of the release agent layer strength and curability, and is preferably 75 or less from the viewpoint of the influence on the peeling force. A more preferred hydroxyl value (mgKOH / g) is 25-60.

In the release agent in the present invention, a commercially available polyolefin polyol can be used. Examples of such commercially available products include Epol (hydroxyl-terminated liquid hydrogenated polyisoprene: Mn = 2500, hydroxyl value = 50.5 mg KOH / g, manufactured by Idemitsu Kosan Co., Ltd.), GI 11000 (hydroxyl-containing liquid hydrogenated polybutadiene: Mn = 1500, hydroxyl value = 60-75 mg KOH / g, manufactured by Nippon Soda Co., Ltd.), Gl-2000 (hydroxyl-containing liquid hydrogenated polybutadiene: Mn = 2100, hydroxyl value = 40-55 mg KOH / g, manufactured by Nippon Soda Co., Ltd.), Gl -3000 (hydroxyl group-containing liquid hydrogenated polybutadiene: Mn = 3000, hydroxyl value = 25 to 35 mgKOH / g, manufactured by Nippon Soda Co., Ltd.). These polyolefin polyols are all liquid at room temperature. Moreover, Unistor P-801 (16 mass% toluene solution of hydroxyl group-containing polyolefin, toluene removal product is solid, hydroxyl value 40 mgKOH / g, manufactured by Mitsui Chemicals, Inc.) can also be used.

In the present invention, the content of polyolefin polyol in the release agent is set so that the value of A in the following formula (Equation 1) is 30 to 250, preferably 40 to 200, more preferably 50 to 150. The If the value of A is less than 30, the strength of the release agent layer tends to be insufficient, and if it exceeds 250, the release force of the release agent layer tends to be too high.

(Equation 1)
A = hydroxyl value of polyolefin polyol (mgKOH / g) × number of parts by weight of polyolefin polyol relative to 100 parts by weight of polyolefin

[Urethane catalyst]

The polyolefin release agent used in the present invention may contain a urethanization catalyst such as an organic tin compound or a metal complex catalyst. This uses one or two or more urethanization catalysts as optional components of the release agent in order to promote the reaction between isocyanate and polyolefin polyol. As the urethanization catalyst, a catalyst used in a usual urethanization reaction can be used, for example, a tin compound such as dibutyltin dilaurate or dioctyltin dilaurate; a carboxylate of a metal such as zinc, cobalt, copper or bismuth; Examples thereof include amine compounds such as 4-diazabicyclo [2.2.2] octane; chelate compounds of metals such as titanium, zirconium, and iron; Moreover, organic acid bismuth salt can also be used as a urethanization catalyst. Examples of the organic acid bismuth salt include abietic acid, neoabietic acid, d-pimalic acid, iso-d-pimalic acid and podocarpic acid, and alicyclic organic acids such as resin acids mainly composed of two or more of these. And bismuth salts of aromatic organic acids such as benzoic acid, cinnamic acid, and P-oxycinnamic acid. Among these, from the viewpoint of compatibility with the release agent component and catalytic activity, dibutyltin dilaurate, dioctyltin dilaurate, bismuth carboxylate and bismuth resinate, and metal chelate compounds such as zirconium and iron are preferable.

When the urethanization catalyst is used, the content thereof is preferably 0.1 to 2.5 parts by mass, more preferably 0.2 to 2.0 parts by mass, and still more preferably 0 with respect to 100 parts by mass of the polyolefin. .3 to 1.5 parts by mass. If this content is less than 0.1 parts by mass, the reaction promoting effect may not be sufficient, and if it exceeds 2.5 parts by mass, the peeling force of the release agent layer to be formed is increased, There may be a problem that the release agent pot life is shortened.

In addition, content of a urethanization catalyst here refers to the quantity of only a urethanization catalyst, for example, when using a commercially available urethanation catalyst solution, the quantity of only the urethanization catalyst except the amount of solvents is meant. Only 1 type may be used for a urethanization catalyst and it may use 2 or more types together. In the release agent of the present invention, the “organotin compound” refers to a compound or salt having a tin-carbon (Sn—C) bond, and examples thereof include dibutyltin dilaurate and dioctyltin dilaurate. In contrast, “non-organotin compound” refers to a compound or salt having no tin-carbon bond.

In the present invention, the “metal complex” refers to a compound or salt having a central metal and a ligand, which are linked by a coordinate bond. This metal complex does not include a mere metal salt having no coordination bond, such as a carboxylic acid metal salt. A metal complex having a coordination bond can exhibit excellent solubility in an organic solvent as compared with a metal salt formed only by an ionic bond. Carboxylic acid metal salts have poor solubility in organic solvents, and also poor solubility in release agent components. Therefore, when a carboxylic acid metal salt is used, the appearance of the coated surface may be deteriorated in the drying step of the applied release agent solution.

From the viewpoint of solubility in an organic solvent, the metal complex catalyst preferably has an organic ligand, and more preferably a metal chelate catalyst. Here, “metal chelate catalyst” refers to a compound or salt in which a metal atom and an organic polydentate ligand form a chelate ring by coordination bond, and “chelate ring” refers to an organic polydentate coordination. A ring structure formed by coordination so that two or more coordinating atoms of a child sandwich a central metal. Examples of the metal chelate catalyst include an acetylacetonato metal complex in which acetylacetone is coordinated to a central metal.

The metal complex catalyst acts to accelerate the urethanization reaction between isocyanate and polyolefin polyol to form a release agent layer having excellent substrate adhesion. From the viewpoint of promoting the reaction, the metal complex catalyst is preferably at least one selected from the group consisting of a titanium complex catalyst, a zinc complex catalyst, a zirconium complex catalyst, an aluminum complex catalyst, and an iron complex catalyst, more preferably a titanium complex catalyst. It is at least one selected from the group consisting of a catalyst, a zinc complex catalyst, a zirconium complex catalyst, and an aluminum complex catalyst. These titanium complex catalyst, zinc complex catalyst, zirconium complex catalyst, aluminum complex catalyst and iron complex catalyst are preferably metal chelate catalysts.

Various metal complex catalysts are commercially available. In the present invention, commercially available metal complex catalysts may be used. Also, various organic ligands, particularly various multidentate ligands that can form metal chelate catalysts are commercially available. Therefore, a metal complex catalyst prepared by combining a commercially available organic ligand and a metal may be used.

Commercially available metal complex catalysts include, for example, titanium chelate catalysts available from Matsumoto Trading Co., Ltd., such as Olgax TC-100 (titanium diisopropoxybis (acetylacetonate)), Olgax TC-401 (titanium tetraacetyl). Acetonate), olgatics TC-200 (titanium dioctyloxybis (octylene glycolate)) and olgatyx TC-750 (titanium diisopropoxybis (ethyl acetoacetate)); zirconium chelate catalyst such as olgatyx ZC- 150 (zirconium tetraacetylacetonate, powder form), ORGATIZ ZC-700 (zirconium tetraacetylacetonate, solution form), ORGATIZ ZC-540 (zirconium tributoxy) Monoacetylacetonate), ORGATIX ZC-570 (zirconium monobutoxyacetylacetonate bis (ethyl acetoacetate)) and ORGATIX ZC-580 (zirconium dibutoxy bis (ethylacetoacetate)); and aluminum chelate complexes such as ORGA Chicks AL-80 (aluminum trisacetylacetonate) and the like are mentioned. Among these, Olgatics TC-401, Olgatics ZC-150 and Olgatyx ZC-700 are preferred, and Olgatics TC-401 is more preferred.

Examples of commercially available metal complex catalysts include zirconium chelate catalysts manufactured by KING INDUSTRIES, such as K-KAT 4205 (zirconium acetylacetonate complex) and K-KAT A209 (zirconium (6-methyl-2,4-heptadionate). ) Complexes); zinc amine catalysts such as K-KAT XK-614 and K-KAT XK-622; and aluminum chelate catalysts such as K-KAT 5218 (aluminum bis (ethylacetoacetate) monoacetylacetonate) Among these, K-KAT 4205, K-KAT A209, K-KAT XK-614 and K-KAT 5218 are preferable, and K-KAT 4205, K-KAT A209 and K-KAT 5218 are more. Mashiku, K-KAT A209 is more preferred.

Commercially available metal complex catalysts include Sunny Cat TC-100 (also called diisopropoxy titanium bis (ethyl acetoacetate) and titanium diisopropoxy bis (ethyl acetoacetate)) manufactured by Nitto Kasei Co., Ltd .; Titanium tetraacetylacetone (also called titanium tetraacetylacetate), titanium tetraheptanedione (also called titanium tetrakis (tetramethylheptanedionate)), zirconium tetraacetylacetone (also called zirconium tetraacetylacetate) and zirconium tetramethylheptanedione; Kawaken Fine chemicals ALCH (aluminum (ethyl acetoacetate) diisopropylate), ALCH-TR ((aluminum tris (ethyl acetoacetate)) )), Aluminum chelate M (aluminum (alkyl acetoacetate) diisopropylate), aluminum chelate D (aluminum bis (ethyl acetoacetate) mono (acetylacetonate)) and aluminum chelate A (W) (aluminum tris (acetylacetonate) )); And tris (ethylacetoaceto) aluminum (also referred to as aluminum tris (aceteracetonate)), tetrakis (2,2,6,6-tetramethyl-3,5-he, manufactured by Wako Pure Chemical Industries, Ltd. Ptandionato) zirconium (IV), iron (III) acetylacetonate and tris (2,2,6,6-tetramethyl-3,5-heptandionato) iron (III); (Aluminum tris (acetylacetonate )), Nursem zirconium (zirconium tetrakis (acetylacetonate)), nursem titanium (titanium diftoxybis (acetylacetonate)), nursem ferric iron (iron (III) trisacetylacetonate), and the like. Of these, nursem ferric is preferred.

The content of the metal complex catalyst in the polyolefin release agent is preferably 0.1 to 2.5 parts by mass, more preferably 0.2 to 2.0 parts by mass, and still more preferably 100 parts by mass of the polyolefin. 0.3 to 1.5 parts by mass. When the content is less than 0.1 parts by mass, the catalytic action may be insufficient. On the other hand, when the content exceeds 2.5 parts by mass, the peeling force of the release agent layer may increase or the peeling may occur. This may cause problems such as shortening the pot life of the agent.

Here, the content of the metal complex catalyst refers to the amount of the metal complex catalyst alone, for example, a catalyst solution in which the metal complex catalyst is dissolved in a solvent such as “K-KAT A209” used in the examples described later. Is used, it means the amount of the metal complex catalyst alone excluding the solvent amount.

[Optional ingredients]

The polyolefin release agent in the present invention may contain one or more optional components. For example, when a release agent layer having a low release force is required, one or more liquid hydrocarbons may be used as an optional component of the release agent. Here, the “liquid hydrocarbon” in the present invention means a carbonization having a viscosity at 38 ° C. (hereinafter sometimes referred to as “38 ° C. viscosity”) of 5 to 1500 Pa · s measured according to JIS K7117-1: 1990. Means hydrogen. By using such a liquid hydrocarbon, it is possible to reduce the speed dependency of the peel strength of the light-transmitting film without reducing the adhesive strength of the adhesive tapes.

The 38 ° C. viscosity of the liquid hydrocarbon is usually 5 to 1500 Pa · s, preferably 5 to 1300 Pa · s. When this 38 degreeC viscosity is less than 5 Pa * s, the speed dependence of peeling force may not fully reduce. That is, in order to sufficiently reduce the speed dependency of the peeling force, when the amount of liquid hydrocarbon having a viscosity at 38 ° C. of less than 5 Pa · s is increased, the photoreactant layer of the photoreactant layer-containing sheet becomes an adhesive. It becomes the tendency for the adhesive force of the photoreaction material layer containing sheet | seat (adhesive sheet) which is a layer to fall. On the other hand, when the viscosity at 38 ° C. exceeds 1500 Pa · s, the fluidity of the liquid hydrocarbon is low at around 10 to 30 ° C., which is the assumed use temperature of the release material and the adhesive tape, and thus the speed dependency of the peeling force is sufficient. May not be reduced.

Examples of liquid hydrocarbons include polymers of unsaturated hydrocarbons. Here, the “polymer of unsaturated hydrocarbon” in the present invention is used to mean not only a polymer but also an oligomer. From the viewpoint of compatibility, the liquid hydrocarbon is preferably a liquid copolymer of ethylene and an unsaturated hydrocarbon having 3 to 5 carbon atoms, a liquid homopolymer of an unsaturated hydrocarbon having 3 to 5 carbon atoms, and a carbon number. It is at least one selected from the group consisting of 3 to 5 unsaturated hydrocarbon liquid copolymers. Examples of the unsaturated hydrocarbon having 3 to 5 carbon atoms include propylene, 1-butene, isobutene, 2-butene, butadiene, 1-pentene, 2-pentene, isopentene, isoprene and the like. The liquid hydrocarbon is more preferably at least one selected from the group consisting of a liquid ethylene-olefin copolymer, liquid polybutadiene, liquid polyisoprene, liquid hydrogenated polybutadiene, liquid hydrogenated polyisoprene, and liquid polyisobutene. The liquid hydrocarbon can be produced by a known method such as radical polymerization or cationic polymerization.

Commercial products may be used as liquid hydrocarbons. Examples of commercially available liquid hydrocarbons include Lucant HC-600 (38 ° C. viscosity = 8.5 Pa · s), HC-2000 (38 ° C. viscosity = 34 Pa · s) (manufactured by Mitsui Chemicals, Inc.), Claprene LIR- 30 (38 ° C. viscosity = 74 Pa · s), LIR-50 (38 ° C. viscosity = 480 Pa · s), LIR-290 (38 ° C. viscosity = 1000 Pa · s), LBR-300 (38 ° C. viscosity = 280 Pa · s) ( As mentioned above, Kuraray Co., Ltd.), Nisseki Polybutene HV-100, HV-300, HV-1900 (above, manufactured by Nippon Oil Corporation), Nissan Polybutene 10N, 30N, 200N (above, made by NOF Corporation), etc. .

When liquid hydrocarbon is used, the content of the release agent in the release agent is preferably 3 to 30 parts by mass, more preferably 4 to 20 parts by mass, and still more preferably 100 parts by mass in total of the polyolefin and the liquid hydrocarbon. Is 5 to 15 parts by mass. When this content is less than 3 parts by mass, the dependency on the peeling rate may not be reduced sufficiently. Conversely, when it exceeds 30 parts by mass, the release agent layer strength is decreased or the photoreactant layer is peeled off. When liquid hydrocarbons migrate from the agent layer and the photoreactive material layer-containing sheet is an adhesive sheet (tape) or the like, the adhesive strength may be reduced.

In the polyolefin-based release agent in the present invention, if necessary, a resin other than the polyolefin, an antioxidant, an ultraviolet absorber, a light stabilizer such as a hindered amine light stabilizer and an antistatic agent, carbon black, calcium oxide, You may contain fillers, pigments, etc., such as magnesium oxide, silica, zinc oxide, and titanium oxide.

[Base film]

The light-transmitting film in the present invention is one in which at least one surface is release-treated with a non-silicone release agent such as the above-described polyolefin-based release agent, and is usually at least one surface of a base film having light transparency. A release agent layer made of a non-silicone release agent is formed.

The base film needs to have optical transparency, and therefore, it is preferably a plastic film having a smooth surface and high transparency. Examples of the plastic film include polyester films such as a polyethylene terephthalate film and a polybutylene terephthalate film; polyolefin films such as a polyethylene film and a polypropylene film; and papers that transmit ultraviolet rays. The base material may be subjected to a treatment such as a corona treatment, a plasma treatment, or a flame treatment in advance as necessary.

The thickness of the base film is not particularly limited and can be appropriately set according to the purpose of use. When a plastic film is used as the substrate film, the thickness is usually about 12 to 250 μm, preferably 16 to 200 μm, more preferably 25 to 125 μm.

[Release layer]

The release agent layer is obtained by dissolving a non-silicone release agent such as the aforementioned polyolefin release agent in an organic solvent to prepare a release agent solution, applying the obtained release agent solution to a substrate film, and drying. It is done.

As an organic solvent, only 1 type may be used and 2 or more types may be used together. The content of the organic solvent is preferably adjusted in the range of 95 to 99.9% by mass in the release agent solution. The organic solvent is not particularly limited as long as it can dissolve the release agent uniformly. However, since the polyolefin release agent contains polyolefin as an essential component, the organic solvent is preferably only one hydrocarbon solvent, a mixed solvent of two or more hydrocarbon solvents, or a hydrocarbon solvent. It is a mixed solvent with other solvents. When a mixed solvent is used, the content of the hydrocarbon solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more in the mixed solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as normal hexane and normal heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene. Examples of other solvents include ketones such as methyl ethyl ketone, cyclohexanone, and acetylacetone, esters such as ethyl acetate, alcohols such as methanol, ethanol, isopropyl alcohol, and tert-butyl alcohol. From the viewpoint of improving the pot life of the release agent solution, a mixed solvent of a hydrocarbon solvent and acetylacetone and a mixed solvent of a hydrocarbon solvent and tert-butyl alcohol are preferable.

The application method of the release agent solution is not particularly limited, and any known method, for example, a method using a kiss roll coater, a pea coater, a rod coater, a Meyer bar coater, a die coater, a gravure coater or the like can be used. There is no particular limitation on the drying method, and any known method can be used. A common drying method is hot air drying. The temperature of hot air drying may vary depending on the heat resistance of the substrate, but is usually about 80 to 150 ° C.

The thickness of the release agent layer after drying is preferably 30 to 500 nm, more preferably 45 to 400 nm, and still more preferably 60 to 300 nm. When this thickness is less than 30 nm, the release force of the release agent layer may be too high. On the other hand, when it exceeds 500 nm, the substrate and the release agent that come into contact with each other when the light-transmitting film is rolled up The problem that it becomes easy to block with a layer and the problem that the peeling force of a light transmissive film become high may arise.

As long as the release agent layer is present on the outermost surface, the light-transmitting film may have another layer between the release agent layer and the base film, but the intermediate layer also has optical transparency. Must be a material. However, the release agent layer is preferably formed directly on the base film.

2. Method for producing photoreactive material layer-containing sheet

In the present invention, the photoreactive material layer-containing sheet is a concept including not only “sheet shape” but also shapes generally called “tape shape”, “film shape” and the like as described above. In addition, the use of the photoreactive material layer in the photoreactive material layer-containing sheet is not particularly limited, and the adhesive layer or the base material of the adhesive tape as described above may be used for various purposes other than these. It can be a layer, a film, or a sheet.

[Adhesive layer]

When the photoreactive material layer is a pressure-sensitive adhesive layer, the photoreactive composition for forming the photoreactive material layer is tacky when the product obtained by photoreacting it (photopolymerization reaction) at 23 ° C. Although it does not restrict | limit in particular, As a typical example, the photopolymerizable composition for acrylic adhesives is mentioned.

As a photopolymerizable composition for an acrylic pressure-sensitive adhesive, a monomer comprising an alkyl acrylate monomer as a main component monomer and a polar group-containing monomer copolymerizable with the alkyl acrylate monomer The photopolymerizable composition which made the body mixture contain the photoinitiator is mentioned.

Examples of the alkyl acrylate monomer include linear, branched or cyclic alkyl groups having 1 to 18 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert, -Butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, cyclohexyl, 3-methylpentyl, n-heptyl, cycloheptyl, n-octyl, 2-ethylhexyl, cyclooctyl, n-nonyl, (Meth) acrylic acid alkyl esters comprising cyclononyl, n-decyl, cyclodecyl, n-undecyl, n-dodecyl, n-tridecyl, etc., preferably a linear or branched alkyl group having 4 to 18 carbon atoms. A linear or cyclic alkyl group (eg n-butyl, isobutyl, ert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, cyclohexyl, 3-methylpentyl, n-heptyl, cycloheptyl, n-octyl, 2-ethylhexyl, cyclooctyl, n-nonyl (Meth) acrylic acid alkyl ester comprising cyclononyl, n-decyl, cyclodecyl, n-undecyl, n-dodecyl, n-tridecyl and the like. One or two or more alkyl acrylate monomers are used.

On the other hand, examples of the polar group-containing monomer include unsaturated acids such as (meth) acrylic acid, itaconic acid, 2-acrylamidopropanesulfonic acid, maleic acid, maleic anhydride, mesaconic acid, citraconic acid, and glutaconic acid; And hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. One or more polar group-containing monomers are used.

In the monomer mixture, the content of the alkyl acrylate monomer as the main component monomer and the polar group-containing monomer is 70 to 100% by mass for the former and 30 to 0% by mass for the latter. The former is particularly preferably 80 to 96% by mass and the latter is 20 to 4% by mass. Outside this range, it is difficult to obtain favorable adhesive properties.

Photopolymerization initiators include benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether and benzyldimethyl ketal, substituted benzoin ethers such as anisole methyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone Substituted acetophenones, substituted alpha-ketols such as 2-methyl-2-hydroxypropiophenone, aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride, 1-phenyl-1,1-propanedione-2- (o-ethoxy) Photoactive oximes such as carbonyl) -oxime, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzof Benzophenone compounds such as non, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone Thioxanthone compounds such as isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s -Triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- Piperonyl-4,6-bis (trichloromethyl) -s-tri Gin, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy -Naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) ) -6-triazine and other triazine compounds; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl) Oxime ester compounds such as -2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenyl ester Phosphine compounds such as sphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; Compound; or titanocene compounds are used. 1 type (s) or 2 or more types are used for a photoinitiator.

The amount of the photopolymerization initiator used is usually 0.1 to 5 parts by mass per 100 parts by mass of the monomer mixture of the aforementioned alkyl acrylate monomer and polar group-containing monomer. When the amount of the photopolymerization initiator is less than this range, the polymerization rate is slow, which is not industrially preferable. When the amount is large, the molecular weight is lowered, and preferable adhesive properties are hardly obtained. The amount of the photopolymerization initiator is preferably 0.1 to 3 parts by mass.

Moreover, a crosslinking agent can be blended in the photopolymerizable composition for the acrylic pressure-sensitive adhesive, if necessary. The cross-linking agent is not particularly limited, but a polyfunctional acrylate monomer is preferable. For example, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, 1,2-ethylene glycol diacrylate, 1,6-hexanediol diacrylate Bifunctional or higher alkyl acrylate monomers such as 1,12-dodecanediol diacrylate are used. The amount of the polyfunctional acrylate monomer used varies depending on the number of functional groups and the like, but is generally 0.01 per 100 parts by mass of the monomer mixture of the alkyl acrylate monomer and the polar group-containing monomer. Is preferably 5 to 5 parts by mass, more preferably 0.1 to 3 parts by mass. When a polyfunctional acrylate monomer is used within this range, a polymer (acrylic pressure-sensitive adhesive) obtained by photopolymerization of the photopolymerizable composition can retain a good cohesive force. Moreover, additives, such as a tackifier, can be mix | blended with a photopolymerizable composition as needed.

[Acrylic urethane base]

When the photoreactive material layer is an acrylic urethane base material, the photoreactive composition for forming the photoreactive material layer is a photopolymerizable composition for the acrylic urethane base material. The photopolymerizable composition is a photoreactive composition in which a product obtained by photoreaction (photopolymerization reaction) does not exhibit tack at 23 ° C.

As a photopolymerizable composition for an acrylic urethane substrate, for example, a composition containing at least a radical polymerizable monomer whose main component monomer is an alkyl acrylate monomer, a urethane polymer, and a photopolymerization initiator is included. Can be mentioned.

Examples of the alkyl acrylate monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, i-butyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl acrylate. , I-octyl acrylate, i-nonyl acrylate, etc., (meth) acrylic acid and linear or branched alcohols having 1 to 10 carbon atoms; isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate , Tricyclodecanyl acrylate, adamantyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, (meth) acrylic acid and 6 carbon atoms And the like; esters of 15 cycloaliphatic alcohols. One or more alkyl acrylate monomers can be used.

The radical polymerizable monomer can contain a monomer other than the alkyl acrylate monomer. Examples of such a monomer include (meth) acrylic acid, itaconic acid, 2-acrylamidopropanesulfonic acid, Unsaturated acids such as maleic acid, maleic anhydride, mesaconic acid, citraconic acid and glutaconic acid; monomers containing hydroxyl groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxybutyl acrylate and hydroxyhexyl acrylate; acetic acid Vinyl ester monomers such as vinyl and vinyl propionate; styrene, acrylamide, methacrylamide, mono- or diester of maleic acid, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, N, N-dimethylaminoethyl Acrylate, N, N-dimethylaminopropylamine methacrylamide, 2-hydroxypropyl acrylate, oligoester acrylate, .epsilon.-caprolactone acrylate, morpholine acrylate, monomers such as methoxylated cyclododecatriene acrylate. One or more monomers other than the alkyl acrylate monomer can be used. Among these, from the viewpoint of compatibility between urethane and acrylic, unsaturated acid is preferable, and acrylic acid is particularly preferable.

The content of the alkyl acrylate monomer in the entire radical polymerizable monomer is not particularly limited, but is preferably 20 to 100% by mass, more preferably 80 to 100% by mass.

The urethane polymer is a polymer obtained by condensation of a polyol and a polyisocyanate, and a catalyst can be used for the reaction between the isocyanate group of the polyisocyanate and the hydroxyl group of the polyol. As the catalyst, for example, a catalyst generally used in urethane reaction such as dibutyltin dilaurate, tin octoate, 1,4-diazabicyclo (2,2,2) octane can be used.

As the polyol, a polyol having two or more hydroxyl groups in one molecule is desirable, and as the low-molecular polyol, divalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, and trimethylolpropane are used. , Trivalent or tetravalent alcohols such as glycerin and pentaerythritol. In addition, examples of the polymer polyol include polyether polyol, polyester polyol, acrylic polyol, and epoxy polyol. In these, polyether polyol and polyester polyol are preferable. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

Examples of the polyester polyol include alcohols such as the aforementioned dihydric alcohols, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol, and dibasic acids such as adipic acid, azelaic acid, and sebacic acid. The polycondensation product is mentioned. In addition, there are lactone ring-opening polymer polyol polycarbonate diol such as polycaprolactone. Examples of the acrylic polyol include a copolymer of a monomer having a hydroxyl group such as hydroxylethyl (meth) acrylate and hydroxypropyl (meth) acrylate, and a copolymer of a hydroxyl group-containing substance and an acrylic monomer. Examples of the epoxy polyol include an amine-modified epoxy resin. These polyols can be used alone or in combination. When strength is required, it is effective to introduce a cross-linked structure with triol or increase the amount of urethane hard segment with low molecular weight diol. When importance is attached to elongation, a diol having a large molecular weight is preferably used alone. Polyether polyols are generally inexpensive and have good water resistance, and polyester polyols have high strength. In the present invention, the type and amount of polyol can be freely selected according to the use and purpose, and also from the viewpoint of urethane reactivity, compatibility with alkyl acrylate monomers, The molecular weight and the amount used can be appropriately selected.

Examples of the polyisocyanate include aromatic, aliphatic or alicyclic diisocyanates, dimers and trimers of these diisocyanates. Aromatic, aliphatic or alicyclic diisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate. 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, butane-1,4-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4 -Diisocyanate, dicyclohexylmethane-4,4-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, Le cyclohexane diisocyanate, m- tetramethylxylylene diisocyanate. Moreover, these dimers, trimers, and polyphenylmethane polyisocyanate are used. Examples of the trimer include isocyanurate type, burette type, and allophanate type. The polyisocyanate may be used alone or in combination of two or more, and the type, combination, etc. of the polyisocyanate may be appropriately selected from the viewpoints of urethane reactivity and compatibility with the alkyl acrylate monomer. From the viewpoint of prompt reaction with the polyol and suppression of the reaction with water, it is preferable to use an alicyclic diisocyanate.

The amount of polyol and polyisocyanate used to form the urethane polymer is not particularly limited. For example, the amount of polyol used is NCO / OH (equivalent ratio) of 0.8 or more with respect to polyisocyanate. Preferably, it is preferably 1 or more. If NCO / OH is less than 0.8, the molecular chain length of the urethane polymer cannot be extended sufficiently, and the strength and elongation tend to decrease.

In the photopolymerization composition, the urethane polymer is preferably present as a (meth) acryloyl group-terminated urethane polymer having a (meth) acryloyl group introduced at the terminal. For this reason, it is preferable to add the hydroxyl compound which has a (meth) acryloyl group in a molecule | numerator in a system after the production | generation reaction of a urethane polymer, and to make this hydroxyl compound react with a urethane polymer. The hydroxyl compound having a (meth) acryloyl group in the molecule may contain one or more (meth) acryloyl groups in the molecule. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Mono (meth) acrylates such as (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate ; Di (meth) acrylates such as trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, glycidol dimethacrylate; pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) Acrylate and the like. In addition, the usage-amount of the hydroxyl compound which has a (meth) acryloyl group in a molecule | numerator is the hydroxyl group (OH) in the said hydroxyl compound with respect to 1 mol of isocyanate groups (NCO) of the polyisocyanate used as a raw material of a urethane polymer. It is selected from the range of about 0.3 to 1.5 mole times, preferably from the range of 0.5 to 1.0 mole times.

As the photopolymerization initiator to be contained in the photopolymerizable composition, the same photopolymerization initiator as that contained in the photopolymerizable composition for an acrylic pressure-sensitive adhesive described above can be used, and specific examples thereof. The above is followed.

The content ratio of the radical polymerizable monomer and the urethane polymer in the photopolymerizable composition for the acrylic urethane base material is not particularly limited, but radicals per 100 parts by mass of the urethane polymer (total amount of polyol and polyisocyanate). The range in which the polymerizable monomer is 5 to 95 parts by mass is preferable, and the range in which the polymerizable monomer is 20 to 80 parts by mass is more preferable. Apart from this range, when the proportion of urethane polymer is large, the resulting acrylic urethane substrate tends to be difficult to obtain sufficient tensile modulus and stress, and when the proportion of radical polymerizable monomer is large, the resulting acrylic It tends to be difficult to obtain sufficient elongation characteristics of the urethane base material.

In the photopolymerizable composition for the acrylic urethane substrate, a crosslinking agent can be blended as necessary. The cross-linking agent is not particularly limited, but a polyfunctional acrylate monomer is preferable. For example, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, 1,2-ethylene glycol diacrylate, 1,6-hexanediol diacrylate Bifunctional or higher alkyl acrylate monomers such as 1,12-dodecanediol diacrylate are used. The amount of the polyfunctional acrylate monomer used is not particularly limited, but is generally selected from the range of 0 to 20 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer.

In addition, the photopolymerizable composition for the acrylic urethane base material, if necessary, additives commonly used for films, such as ultraviolet absorbers, anti-aging agents, fillers, pigments, colorants, flame retardants, An antistatic agent or the like can be added.

These additives are used in normal amounts depending on the type. These additives may be added in advance before the polymerization reaction of the polyisocyanate and the polyol, or added before the urethane polymer and the hydroxyl compound having a (meth) acryloyl group in the molecule are polymerized. May be. Moreover, you may add a small amount of solvent to the photopolymerizable composition for acrylic urethane base materials for the viscosity adjustment of coating. The solvent can be appropriately selected from commonly used solvents, and examples thereof include ethyl acetate, toluene, chloroform, dimethylformamide and the like.

In the present invention, the photoreactive composition for forming the photoreactive material layer is not limited to the above-described photopolymerizable composition for pressure-sensitive adhesives and photopolymerizable composition for acrylic urethane substrates, but various uses. The photoreactive composition in can be applied.

In the photoreactive material layer-containing sheet of the present invention, a photoreactive composition layer was formed on at least one side of a support, and the outer surface of the photoreactive composition layer was subjected to a release treatment with a non-silicone release agent. The photoreactive composition layer is formed on the release agent layer of the light-transmitting film which is overlaid with the release layer of the light-transmitting film or is subjected to the release treatment with the non-silicone release agent. After the support is stacked on the physical layer, it can be produced by irradiating light to form a photoreactive material layer in which the photoreactive composition layer is photoreacted.

At this time, the formation of the photoreactive composition layer on at least one side of the support or on the release agent layer of the light transmissive film can be performed by applying the photoreactive composition. Examples of the coating method include a die coater, a roll coater, a roll knife coater, a lip coater, a closed edge die coater, a gravure coater, a curtain coater, and a CAP coater.

The support may be a material that transmits light or a material that does not transmit light. Specifically, a polyimide film, a polyester film, a polytetrafluoroethylene film, a polyether ether ketone film, a polyether sulfone film, a polyethylene film, a polypropylene film, paper, or the like is used. Moreover, a mold release process can be given to this support body as needed.

The photoreactive material layer-containing sheet of the present invention supports a light-transmitting film that has been subjected to a release treatment with a release agent in order to prevent contamination of light irradiation means by an unreacted photoreactive composition and a decrease in light illuminance. After bonding to the surface of the body coated with the photoreactive composition layer, the surface of the support to which the light transmissive film is bonded is irradiated with light from the light irradiation means, and the photoreactive composition undergoes photoreaction. It is preferable to manufacture the light-transmitting film in a mode in which the light-transmitting film is peeled off from the support after the necessary light irradiation is completed.

The light-transmitting film acts on the photoreactive composition layer while transmitting light, while the unreacted photoreactive composition is blocked by the light-transmitting film and adheres to the light-transmitting film. Contamination of the light irradiation means by the reaction photoreactive composition and a decrease in light illuminance can be prevented. In particular, when the photoreactive composition layer is a photoreactive composition layer that is photopolymerized by light from the light irradiation means to form a pressure-sensitive adhesive layer, the photoreaction of the photoreactive composition layer ( Unreacted monomer evaporates with photopolymerization), but this monomer is blocked by the light-transmitting film and adheres to the light-transmitting film, thereby preventing contamination of the light irradiation means by the monomer and a decrease in light illuminance. Can do. Moreover, when peeling a light transmissive film from a support body, only a light transmissive film peels in the state which the photoreactive composition layer was closely_contact | adhered to the support body.

The “light” in the light irradiation in the present invention is usually ultraviolet light, and an ultraviolet irradiation lamp is used for the light irradiation device, which emits light in the same region as the absorption wavelength of the photopolymerization initiator. It is done. For example, LEDs, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, microwave-excited mercury lamps, black light lamps, chemical lamps, sterilizing lamps, low-pressure discharge mercury lamps, excimer lasers, etc. There is no particular limitation as long as it is rod-shaped. Moreover, you may combine those one or two or more light sources. In addition, the irradiation of the ultraviolet rays (light) by the ultraviolet irradiation lamp is performed from the light transmissive film side when the support is not light transmissive, and when the support is light transmissive, the light transmissive film side and It can carry out from either side from either one side of a support body side.

In addition, it is desirable to irradiate ultraviolet rays (light) after cutting short wavelength light of about 300 nm or less with a filter. Examples of such a filter include Pyrex (registered trademark) glass and soda glass. By irradiating with the short wavelength light cut, there is an effect of suppressing deterioration due to repeated use of the light transmissive film or suppressing heavy peeling. Further, when the lamp has a large amount of heat generation or polymerization heat, an ultraviolet cut filter or a cooling device can be used. In this case, the cooling is preferably performed at a temperature lower than the transition start temperature to the glass transition region of the light transmissive film. By setting the transition start temperature or lower, it is possible to prevent the film from being stretched or wrinkled during repeated use of the light transmissive film. When the photoreactive composition is a photopolymerizable composition, the intensity of light applied to the photoreactive composition coating layer by the ultraviolet irradiation lamp is a factor that determines the degree of polymerization of the resulting polymer. It is preferably 0.1 to 300 mW / cm ² , and more preferably 1 to 50 mW / cm ² .

The photoreactive material layer-containing sheet of the present invention can easily peel the light transmissive film from the photoreactive material layer without using a silicone release agent for the release treatment of the light transmissive film. It is an important technical feature that the peeling force of the photosensitive film to the photoreactive material layer is 1.0 N / 25 mm or less. The peeling force is preferably 0.7 N / 25 mm or less, more preferably 0.5 N / 25 mm or less (the lower limit value of the peeling force is preferably 0.01 N / 25 mm or more). In the present invention, the peel strength of the light-transmitting film with respect to the photoreactive material layer is determined by cutting the photoreactive material layer-containing sheet into a width of 25 mm, and using a tensile tester, peeling angle: 180 °, tensile speed: 10 m / min. , Peeling surface: a value measured in an atmosphere at 23 ° C. on the condition of the light transmissive film (release material) side.

In addition, since no silicone release agent is used as the release agent, the amount of silicone component deposited on the surface of the photoreactive material layer on which the light-transmitting film is bonded is less than 1.0 [kcps]. In the present invention, the silicone component adhesion amount is a value measured based on the method described later.

3. Physical properties, properties, etc. The physical properties, properties, etc. in this specification are measured values by the following methods.
(1) Density This is a value measured according to ASTM D1505.
(2) Melt flow rate (230 ° C)
It is a value measured according to ASTM D1238.
(3) Number average molecular weight It is the value measured based on ASTM D2503.
(4) Hydroxyl value A value measured in accordance with JIS K1557: 1970.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but these do not limit the present invention. In the following, “part” and “%” represent “part by mass” and “% by mass”, respectively, unless otherwise specified.

<Examples 1 to 20 and Comparative Examples 1 to 6>
1. Release agent component The release agent components used in Examples 1 to 20 are described below.

(1) Polyolefin Toughmer A-1070S (ethylene-1-butene random copolymer (ethylene: 85 mol%, 1-butene: 15 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 2.2 g / 10 min , Density: 0.87 g / cm ³ , tensile elastic modulus at 23 ° C .: 4.7 MPa, tensile fracture stress at 23 ° C .: 11.3 MPa)

Tuffmer P-0280 (ethylene-propylene copolymer (ethylene: 87 mol%, propylene: 13 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 5.4 g / 10 min, density: 0.87 g / cm ³ , Tensile elastic modulus at 23 ° C .: 5.1 MPa, tensile fracture stress at 23 ° C .: 3.3 MPa)

TAFMER A-3570S (ethylene-1-butene copolymer (ethylene: 85 mol%, 1-butene: 15 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 65 g / 10 min, density: 0.87 g / cm ³ , tensile elastic modulus at 23 ° C .: 3.5 MPa, tensile fracture stress at 23 ° C .: 2.1 MPa)

TAFMER XM-7070 (propylene-1-butene copolymer (propylene: 74 mol%, 1-butene: 26 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 7 g / 10 min, density: 0.87 g / cm ³ , tensile elastic modulus at 23 ° C .: 42.1 MPa, tensile fracture stress at 23 ° C .: 15.4 MPa)

(2) Polyolefin polyol Epol (hydroxyl-terminated liquid hydrogenated polyisoprene, Mn: 2500, hydroxyl value: 50.5 mgKOH / g, manufactured by Idemitsu Kosan Co., Ltd.)

(3) Isocyanate Coronate L (75% ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate, number of isocyanate groups in one molecule: 3, manufactured by Nippon Polyurethane)

(4) Liquid hydrocarbon Lucant HC-2000 (ethylene-α-olefin co-oligomer, 38 ° C. viscosity: 34 Pa · S, manufactured by Mitsui Chemicals)

(5) Metal complex catalyst K-KAT A209 (zirconium (6-methyl-2,4-heptandionate) complex solution, metal complex content: about 14%, manufactured by KING lNDUSTRIES)
Nursem ferric (iron (Ill) trisacetylacetonate, manufactured by Nippon Chemical Industry Co., Ltd.)

(6) Organic solvent Toluene tert-Butyl alcohol Acetylacetone

2. Production of light transmissive film The light transmissive film used in Examples 1 to 20 was produced by the following method.
Using a Mayer bar # 6, the release agent solution was applied to a 38 μm thick polyester film (Lumirror S-10, manufactured by Toray Industries, Inc.) and then heated with a hot air dryer at 130 ° C. for 1 minute to obtain a release agent layer (thickness) A light transmissive film having a thickness of about 150 nm) was produced.

In Comparative Examples 1 to 6, the following three types of light-transmitting films subjected to release treatment were used.
Light-transmitting film for comparison 1: Diafoil MRF (thickness 38 μm, manufactured by Mitsubishi Plastics, treated with silicone release agent)
Light transmissive film for comparison 2: Diafoil MRE (thickness 38 μm, manufactured by Mitsubishi Plastics, treated with silicone release agent)
Light-transmitting film for comparison 3: Ashioresin RA-95H (long-chain alkyl release agent) manufactured by Ashio Sangyo Co., Ltd. coated on a PET substrate (thickness 38 μm) to a thickness of about 40-50 nm.

Comparative Examples 1 and 4 used the comparative light transmissive film 1, Comparative Examples 2 and 5 used the comparative light transmissive film 2, and Comparative Examples 3 and 6 used the comparative light transmissive film 3. .

3. Evaluation of Release Agent Layer Characteristics (1) A photoreactive material layer-containing sheet was prepared by the following method.
Using photo-reactive composition on each light-transmitting film using a baker-type applicator or a doctor blade type applicator, the photo-reactive material layer (acrylic adhesive layer) after photo-reaction has a thickness of about 100 μm. The photoreacted material layer (acrylic urethane base material) was coated so that the thickness was about 200 μm, and PET (# 38, Lumirror S-10, manufactured by Toray Industries, Inc.) was bonded to the opposite side. The sample was irradiated with black light from the light transmissive film side at an illuminance of 6.3 mW / cm ² and a light amount of 340 mJ / cm ² · min for 5 minutes to carry out a photoreaction.

As the photoreactive composition, a photopolymerizable composition for an acrylic pressure-sensitive adhesive (Experimental Example 1 described later) and a photopolymerizable composition for an acrylic urethane substrate (Experimental Example 2 described later) were used.

(2) Peeling force after irradiation with black light The peeling force when peeling the light transmissive film from the photoreactive composition layer (photoreactive material layer) after photoreaction was measured, and the values were compared. Cut into a width of 25 mm and stored at 23 ° C. for 0.5 to 1.0 hours after irradiation with black light. Using a tensile tester, peeling angle: 180 °, tensile speed: 10 m / min, peeling surface: release material side, The peeling force in a 23 ° C. atmosphere was measured under the conditions. Moreover, the reference | standard of the peelable peel force in this case was 1.0 N / 25mm or less.

(3) Silicone component transfer amount to the photoreactive material layer Silicone component to the photoreactive material layer when the light transmissive film is peeled off from the photoreactive material layer obtained by photoreacting the photoreactive composition layer The amount of migration (adhesion) was confirmed by X-ray fluorescence (XRF) measurement.
Measurement conditions were evaluated by the amount of silicone component in a circular peeled area with a diameter of 30 mmφ using an XRF analyzer (ZSX100e) manufactured by Rigaku (X-ray source: vertical Rh tube, analytical element: Si, spectral crystal: RX4, output: 50 kV, 70 mA).

(4) Experiment 1 (Examples 1 to 9, Comparative Examples 1 to 3)
[Preparation of acrylic pressure-sensitive adhesive (photoreactive composition)]
Four parts by weight of 2-ethylhexyl acrylate (2EHA) 90 parts by mass, acrylic acid (AA) 10 parts by weight and 2,2-dimethoxy-2-phenylacetophenone 0.05 parts by weight as a photopolymerization initiator A partially photopolymerized syrup was obtained by exposure to ultraviolet light under a nitrogen atmosphere. To 100 parts by mass of this partially polymerized syrup, 0.3 part by mass of trimethylolpropane triacrylate was uniformly mixed as a crosslinking ratio to obtain a photoreactive composition.

[Preparation of release agent solution]
Each component was mixed in the number of parts shown in Table 1. Examples 1, 2 and 6 were mixed solvents of toluene and acetylacetone (toluene / acetylacetone mass ratio = 99.1 / 0.9). ~ 5 and 7-9 are dissolved in a mixed solvent of toluene and tert-butyl alcohol (mass ratio of toluene / tert-butyl alcohol = 95/5) to prepare a release agent solution having a solid content of 1.5%. did. The number of parts of the catalyst shown in Table 1 is the number of parts of the obtained catalyst itself, and when the obtained catalyst is a solution, it is the number of parts of the entire catalyst solution.

From Table 1, the release property of the light-transmitting film which was release-treated with the polyolefin release agent for the photoreactive material layer (acrylic pressure-sensitive adhesive layer) obtained by photoreacting the photoreactive composition was determined to be silicone. Compared to the light-transmitting film release-treated with the release agent, the release film is slightly heavier than the light-transmitting film released with the polyolefin release agent. It is a peelable level that can be peeled off. On the other hand, in Comparative Example 3 using a light-transmitting film which has been subjected to a release treatment with a long-chain alkyl release agent, the light-transmitting film is remarkably heavy and has a level of releasability that is difficult to peel. Further, in Comparative Examples 1 and 2 using a light-transmitting film which has been release-treated with a silicone release agent, a photoreactive material layer (acrylic) obtained by photoreacting the photoreactive composition based on the results of XRF analysis. It was confirmed that the silicone component migrated to the surface of the pressure-sensitive adhesive layer). Therefore, it was confirmed that the light-transmitting film which was release-treated with the polyolefin-based release agent was a light-transmitting film having good releasability and no migration of the silicone component.

(5) Experiment 2 (Examples 10 to 20, Comparative Examples 4 to 6)
[Preparation of acrylic urethane substrate (photoreactive composition)]
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n-butyl acrylate (BA, manufactured by Toagosei Co., Ltd.) ): 19 parts by weight, acrylic acid (AA): 10 parts by weight, polybutylene adipate having a number average molecular weight of 1000 as a polyol (trade name “Nipporan” 4009, manufactured by Nippon Polyurethane Industry Co., Ltd.): 76.9 parts by weight, dilaurin as a catalyst Dibutyltin acid (DBTL): Add 0.01 parts by weight, and while stirring, add 18.7 parts by weight of hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethanes) and react at 65 ° C. for 5 hours. A urethane polymer-monomer mixture was obtained. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 4.4 parts by weight were added and reacted at 65 ° C. for 1 hour to obtain an acryloyl group-terminated urethane polymer-monomer mixture. .

To the resulting acryloyl group-terminated urethane polymer-monomer mixture, bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide (trade name “Irgacure 819”, manufactured by BASF Corporation) as a photopolymerization initiator: 0.15 A photoreactive composition was obtained by adding parts by weight.

[Preparation of release agent solution]
Each component was mixed in the number of parts shown in Table 2, and this mixture was dissolved in a mixed solvent of toluene and tert-butyl alcohol (mass ratio of toluene / tert-butyl alcohol = 95/5). A 5% release agent solution was prepared. The number of parts of the catalyst shown in Table 2 is the number of parts of the obtained catalyst itself, and when the obtained catalyst is a solution, it is the number of parts of the entire catalyst solution.

From Table 2, the releasability of the light-transmitting film which has been release-treated with the polyolefin-based release agent for the photoreactive material layer (acrylic urethane substrate) obtained by photoreacting the photoreactive composition is silicone-based. Compared to the light-transmitting film that has been release-treated with a release agent, the release is somewhat heavy, but the light-transmitting film that has been release-treated with a polyolefin release agent is also peeled off from the photoreactant layer (acrylic urethane substrate). This is the level of peelability possible. On the other hand, in Comparative Example 6 using a light-transmitting film that has been subjected to a release treatment with a long-chain alkyl release agent, the light-transmitting film is remarkably heavy and has a level of releasability that is difficult to peel. Moreover, in Comparative Examples 4 and 5 using a light-transmitting film which was release-treated with a silicone-based release agent, a photoreactive material layer (acrylic) obtained by photoreacting the photoreactive composition based on the results of XRF analysis. Urethane substrate) The silicone component was transferred to the surface. Therefore, it was confirmed that the light-transmitting film which was subjected to the release treatment with the polyolefin-based release agent was a light-transmitting film having the releasability and having no silicone component migration.

In a photoreactive material layer-containing sheet in which a light-transmitting film that has been subjected to a release treatment with a polyolefin-based release agent is bonded to at least one surface of a photoreactive material layer obtained by photoreaction of a photoreactive composition, For example, when the photoreactive material-containing sheet is a pressure-sensitive adhesive sheet or pressure-sensitive adhesive tape that includes a pressure-sensitive adhesive layer as a photoreactive material layer, It can be suitably used for applications.

This application is based on Japanese Patent Application No. 2012-157924 filed in Japan, the contents of which are incorporated in full herein.

Claims

A photoreactive material layer-containing sheet in which a light transmissive film subjected to a release treatment with a non-silicone release agent is bonded to at least one surface of a photoreactive material layer obtained by photoreacting a photoreactive composition,
A photoreactive material layer-containing sheet, wherein a peel strength of the light transmissive film with respect to the photoreactive material layer is 1.0 N / 25 mm or less.
The photoreactive material layer-containing sheet according to claim 1, wherein the amount of the silicone component attached to the surface of the photoreactive material layer on which the light transmissive film is bonded is less than 1.0 [kcps].
The photoreactant layer-containing sheet according to claim 1 or 2, wherein the non-silicone release agent is a polyolefin release agent containing at least polyolefin, isocyanate and polyolefin polyol.
The photoreactive material layer-containing sheet according to claim 3, wherein the polyolefin release agent further contains a urethanization catalyst.
The photoreactant layer-containing sheet according to claim 4, wherein the urethanization catalyst is a metal complex catalyst or / and an organotin catalyst.
The polyolefin content in the release agent is 80% by mass or more, and 90% by mass or more of the polyolefin is a polyolefin having a tensile elastic modulus at 23 ° C. of 10 MPa or less and a tensile fracture stress at 23 ° C. of 15 MPa or less. Item 6. The photoreactive material layer-containing sheet according to any one of Items 3 to 5.
The photoreactive material layer-containing sheet according to claim 6, wherein the photoreactive composition is a photopolymerizable composition for pressure-sensitive adhesives, and the photoreactive material layer is a pressure-sensitive adhesive layer.
The photopolymerizable composition for pressure-sensitive adhesives is photopolymerized into a monomer mixture containing an alkyl acrylate monomer as a main component monomer and a polar group-containing monomer copolymerizable with the alkyl acrylate monomer. The photoreaction product layer-containing sheet according to claim 7, which is a photopolymerizable composition for an acrylic pressure-sensitive adhesive containing an initiator.
9. The monomer mixture is composed of 70 to 100% by mass of an alkyl acrylate monomer having an alkyl group having 1 to 18 carbon atoms and 30 to 0% by mass of a polar group-containing monomer. Photoreactive substance layer-containing sheet.
The polyolefin content in the release agent is 80% by mass or more, 90% by mass or more of the polyolefin is a polyolefin having a tensile elastic modulus at 23 ° C. of 25 MPa or more and a tensile fracture stress at 23 ° C. of 8 MPa or more. Item 6. The photoreactive material layer-containing sheet according to any one of Items 3 to 5.
The photoreactive material layer-containing sheet according to claim 10, wherein the photoreactive composition is a photopolymerizable composition for an acrylic urethane substrate, and the photoreactive material layer is an acrylic urethane substrate.
The photopolymerizable composition for an acrylic urethane substrate is a composition comprising a radical polymerizable monomer whose main component monomer is an alkyl acrylate monomer, a urethane polymer, and a photopolymerization initiator. The photoreaction material layer containing sheet | seat of description.
The photoreactive material layer-containing sheet according to any one of claims 1 to 12, wherein the light-transmitting film is a polyester film.
A photoreactive composition layer is formed on at least one side of a support, and a release agent layer of a light-transmitting film which has been subjected to a release treatment with a non-silicone release agent is superimposed on the outer surface of the photoreactive composition layer. Alternatively, after forming a photoreactive composition layer on the release agent layer of the light-transmitting film that has been release-treated with the non-silicone release agent, and laminating the support on the photoreactive composition layer, Is a method for producing a photoreactive material layer-containing sheet, which forms a photoreactive material layer obtained by photoreacting the photoreactive composition layer.
The method for producing a photoreactant layer-containing sheet, wherein the non-silicone release agent is a polyolefin release agent containing at least polyolefin, isocyanate and polyolefin polyol.
The method according to claim 14, wherein the polyolefin release agent further contains a urethanization catalyst.
The method according to claim 15, wherein the urethanization catalyst is a metal complex catalyst or / and an organotin catalyst.
The method according to any one of claims 14 to 16, wherein the photoreactive composition is a photopolymerizable composition for pressure-sensitive adhesive, and the photoreactive material layer is a pressure-sensitive adhesive layer.
The polyolefin content in the polyolefin release agent is 80% by mass or more, and 90% by mass or more of the polyolefin is a polyolefin having a tensile elastic modulus at 23 ° C. of 10 MPa or less and a tensile fracture stress at 23 ° C. of 15 MPa or less. The method of claim 17.
The photopolymerizable composition for pressure-sensitive adhesives is applied to a monomer mixture containing an alkyl acrylate monomer as a main component monomer and a polar group-containing monomer copolymerizable with the alkyl acrylate monomer. The method according to claim 17 or 18, wherein a polymerization initiator is contained.
The monomer mixture is composed of 70 to 100% by mass of an alkyl acrylate monomer having 1 to 18 carbon atoms in an alkyl group and 30 to 0% by mass of a polar group-containing monomer. the method of.
The method according to any one of claims 14 to 16, wherein the photoreactive composition is a photopolymerizable composition for an acrylic urethane substrate, and the photoreactive material layer is an acrylic urethane substrate.
The photopolymerizable composition for an acrylic urethane substrate is a composition comprising a radical polymerizable monomer whose main component monomer is an alkyl acrylate monomer, a urethane polymer, and a photopolymerization initiator. The method described.
The polyolefin content in the polyolefin release agent is 80% by mass or more, and 90% by mass or more of the polyolefin is a polyolefin having a tensile elastic modulus at 23 ° C. of 10 MPa or less and a tensile fracture stress at 23 ° C. of 15 MPa or less. The method of claim 22.
A photoreactive material layer-containing sheet produced by the method according to any one of claims 14 to 23.