JP6323851B2 - Photoreactive material layer-containing sheet and method for producing the same - Google Patents

Description

  The present invention is a photoreactive material layer obtained by laminating a support, a photoreactive material layer obtained by photoreacting a photoreactive composition, and a light transmissive film having a release agent layer on a base film in this order. It is related with a content sheet and its manufacturing method.

  Conventionally, a sheet (photoreactive material layer-containing sheet) including a photoreactive material layer formed by photoreacting a photoreactive composition on a support such as a sheet has been widely produced. Examples of such a photoreactive material layer-containing sheet include a pressure-sensitive adhesive sheet provided with an acrylic pressure-sensitive adhesive layer containing an acrylic polymer obtained by polymerization by light irradiation. Such a photoreactant layer-containing sheet such as a pressure-sensitive adhesive sheet is not only excellent in weather resistance, heat resistance, and chemical resistance, but also an organic solvent that causes air pollution, which has recently become a problem. It has the advantage that it can be manufactured without use.

  However, for example, the photopolymerization reaction caused by light irradiation has a problem of polymerization inhibition due to oxygen. As a method for preventing this polymerization inhibition, a method of performing a photopolymerization reaction in a nitrogen atmosphere is known (for example, Patent Document 1). reference). As another method, the photoreactive composition coating layer formed on the support is covered with a light-transmitting film that has been subjected to a release treatment so that the coating layer is shielded from oxygen, and then the light is applied. A method of irradiating light to the coating layer through a transmissive film is known (for example, see Patent Document 2).

JP 2002-138258 A JP 2004-322408 A

  In the photopolymerization reaction in a nitrogen atmosphere described in Patent Document 1, since oxygen does not exist in the polymerization atmosphere, the problem of polymerization inhibition is solved, but the photoreactive composition is not reacted from the coating layer during light irradiation. There has been a problem that components (for example, monomer components) are volatilized and the composition of the coating layer is changed, or the light irradiation means is contaminated by the volatilized components. Further, when trying to avoid such a problem of contamination, there is also a problem that the equipment cost of the light irradiation zone becomes expensive.

  Further, in the method using the light-transmitting film of Patent Document 2, since the coating layer of the photoreactive composition can be shielded from oxygen, the problem of polymerization inhibition has been solved. However, in the method described in Patent Document 2, since the photopolymerization is performed in a state where the light transmissive film and the photoreactive composition coating layer are in contact with each other, the peeling force of the light transmissive film with respect to the photoreactive material layer is large. It became too much (heavy peeling). One of the causes of such heavy release is thought to be the reaction between the remaining functional groups in the silicone-treated layer (release agent layer) of the light transmissive film and the functional groups in the photoreactive composition coating layer. It is done. When the light transmissive film is heavyly peeled off, it becomes difficult to peel the light transmissive film from the photoreactive material layer, and when the light transmissive film is forcibly peeled, the photoreactive material layer is deformed.

  Furthermore, in Patent Document 2, no examination has been made on the peeling force between the support and the photoreactive material layer, but if the peeling force between the support and the photoreactive material layer is too small, the light-transmitting film is peeled off. In doing so, there was also a problem that the photoreactive material layer peeled off from the support.

  Therefore, the present invention provides a photoreaction in which a support, a photoreactive material layer obtained by photoreacting a photoreactive composition, and a light-transmitting film having a release agent layer on a substrate film are bonded in this order. It is a material layer-containing sheet, and the peeling property of the light transmissive film with respect to the photoreactive material layer is not excessively increased, and the light transmissive film is formed into a photoreactive material without deforming the photoreactive material layer when necessary. It can be easily peeled off from the layer, and the photoreactive material layer is not peeled off from the support when the light transmissive film is peeled off. An object of the present invention is to provide a photoreactive material layer-containing sheet in which the photoreactive material layer does not peel from the support. Another object of the present invention is to provide a method for producing a photoreactant-containing sheet.

  As a result of extensive studies by the present inventors, a light transmissive film having a release agent layer formed of a specific addition-type silicone release agent composition is in contact with an application layer formed from the photoreactive composition. The present invention was completed by discovering that even if a photoreaction was carried out in this state, the photoreactive material layer obtained after the photoreaction would not undergo heavy peeling, and further research was carried out based on this finding.

（式中、ｎは、２〜１０の整数である）
で示される官能基を有するポリオルガノシロキサン、及び、分子中にヒドロシリル基を有するポリオルガノシロキサン架橋剤を含有する、付加型シリコーン系剥離剤組成物から形成されたものであり、
前記光透過性フィルムの光反応物層に対する剥離力が、０．５Ｎ／５０ｍｍ以下であり、
前記支持体の光反応物層に対する剥離力が、光透過性フィルムの光反応物層に対する剥離力より高いことを特徴とする、光反応物層含有シートに関する。 That is, in the present invention, a support, a photoreactive material layer obtained by photoreacting a photoreactive composition, and a light transmissive film having a release agent layer on a base film are bonded in this order. The photoreactive material layer-containing sheet in which the release agent layer of the light transmissive film and the photoreactive material layer are in contact with each other,
In the molecule, the release agent layer has the general formula (1):

(In the formula, n is an integer of 2 to 10)
Formed from an addition-type silicone release agent composition containing a polyorganosiloxane having a functional group represented by the formula (1) and a polyorganosiloxane crosslinking agent having a hydrosilyl group in the molecule,
The peeling force with respect to the photoreactive material layer of the light transmissive film is 0.5 N / 50 mm or less,
It is related with the photoreaction material layer containing sheet | seat characterized by the peeling force with respect to the photoreactive material layer of the said support body being higher than the peeling force with respect to the photoreaction material layer of a transparent film.

  It is preferable that 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 adhesive comprises a monomer component containing an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and a monomer copolymerizable with the alkyl (meth) acrylate, and a photopolymerization initiator It is preferable that it is a photopolymerizable composition for acrylic adhesives containing.

  The monomer component preferably contains 70 to 100% by mass of an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and 30 to 0% by mass of a copolymerizable monomer.

  The base film is preferably a polyester film.

  It is preferable that the support is a release film that has been subjected to a release treatment, and the release treatment surface of the support is in contact with the photoreactant layer.

（式中、ｎは、２〜１０の整数である）
で示される官能基を有するポリオルガノシロキサン、及び、分子中にヒドロシリル基を有するポリオルガノシロキサン架橋剤を含有する、付加型シリコーン系剥離剤組成物から形成されたものであることを特徴とする、光反応物層含有シートの製造方法に関する。 Further, the present invention provides a support, a coating layer formed from the photoreactive composition, and a light transmissive film having a release agent layer on the base film in this order, and the light transmissive film. Forming a laminate in which the release agent layer and the coating layer are in contact with each other;
Irradiating the laminate with light to photoreact the coating layer formed from the photoreactive composition to form a photoreactive material layer,
In the molecule, the release agent layer has the general formula (1):

(In the formula, n is an integer of 2 to 10)
A polyorganosiloxane having a functional group represented by the formula (1) and a polyorganosiloxane crosslinker having a hydrosilyl group in the molecule, which is formed from an addition-type silicone release agent composition, The present invention relates to a method for producing a photoreactive material layer-containing sheet.

  It is preferable that 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 adhesive comprises a monomer component containing an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and a monomer copolymerizable with the alkyl (meth) acrylate, and a photopolymerization initiator It is preferable that it is a photopolymerizable composition for acrylic adhesives containing.

  The monomer component preferably contains 70 to 100% by mass of an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and 30 to 0% by mass of a copolymerizable monomer.

  The base film is preferably a polyester film.

  It is preferable that the support is a release film that has been subjected to a release treatment, and the release treatment surface of the support is in contact with the photoreactant layer.

  Furthermore, this invention relates to the photoreaction material layer containing sheet manufactured with the said manufacturing method.

  Since the photoreactive material layer-containing sheet of the present invention uses a light-transmitting film having a specific release agent layer, even if a photoreaction is made in contact with the coating layer formed from the photoreactive composition. The light-transmitting film can be easily peeled from the photoreactive material layer without excessively increasing the peeling force of the light-transmitting film with respect to the photoreactive material layer and without deforming the photoreactive material layer when necessary. Can do. Moreover, since the peeling force with respect to the photoreactive material layer of a support body is higher than the peeling force with respect to the photoreactive material layer of a light transmissive film, the photoreactive material layer containing sheet | seat of this invention is when peeling a light transmissive film. The photoreactive material layer does not peel off from the support, and the photoreactive material layer does not peel off from the support until the photoreactive material layer is used for the intended application.

It is a schematic sectional drawing which shows an example of the photoreaction material layer containing sheet | seat of this invention.

（式中、ｎは、２〜１０の整数である）
で示される官能基を有するポリオルガノシロキサン、及び、分子中に官能基としてヒドロシリル基を有するポリオルガノシロキサン架橋剤を含有する、付加型シリコーン系剥離剤組成物から形成されたものであり、
前記剥離剤層３を有する光透過性フィルム４の光反応物層５に対する剥離力が、０．５Ｎ／５０ｍｍ以下であり、
前記支持体６の光反応物層５に対する剥離力が、光透過性フィルム４の光反応物層５に対する剥離力より高いことを特徴とするものである。なお、本発明の光反応物層含有シートの形状は、「シート状」だけでなく、一般に「テープ状」、「フィルム状」等と呼ばれる形状のものも包含する概念である。 1. Photoreactant layer-containing sheet The photoreactor layer-containing sheet of the present invention will be described with reference to FIG. The photoreactive material layer-containing sheet 1 of the present invention includes a support 6, a photoreactive material layer 5 obtained by photoreacting a photoreactive composition, and a light transmissive film having a release agent layer 3 on a base film 2. 4 is a photoreactive material layer-containing sheet in which the release agent layer 3 of the light transmissive film 4 and the photoreactive material layer 5 are in contact with each other,
In the molecule, the release agent layer 3 has the general formula (1):

(In the formula, n is an integer of 2 to 10)
A polyorganosiloxane having a functional group represented by the formula (1) and a polyorganosiloxane crosslinking agent having a hydrosilyl group as a functional group in the molecule, and formed from an addition-type silicone release agent composition,
The peeling force with respect to the photoreactive material layer 5 of the light transmissive film 4 having the release agent layer 3 is 0.5 N / 50 mm or less,
The peeling force of the support 6 with respect to the photoreactive material layer 5 is higher than the peeling force of the light transmissive film 4 with respect to the photoreactive material layer 5. 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.

  Since the photoreactive material layer-containing sheet of the present invention uses a light-transmitting film having a specific release agent layer on a base film, the light-transmitting film and a coating layer formed from the photoreactive composition are included. Even if a photoreaction is performed in a contact state, the light transmissive film can be easily peeled off from the photoreactant layer. That is, it is an important technical feature that the peel strength of the light transmissive film with respect to the photoreactive material layer is 0.5 N / 50 mm or less. The peeling force is preferably 0.4 N / 50 mm or less, and more preferably 0.3 N / 50 mm or less. Further, the lower limit value of the peeling force is not particularly limited, but is preferably 0.01 N / 50 mm or more. The peeling force is measured by the method described in the examples.

  In the photoreactive material layer-containing sheet of the present invention, the support is laminated on the surface opposite to the surface of the photoreactive material layer on which the light transmissive film is laminated. Another feature is that the peel force for the reactant layer is higher than the peel force for the light reactant layer of the light transmissive film. The peel strength of the support with respect to the photoreactive material layer is preferably 0.1 N / 50 mm or higher, more preferably 0.2 N / 50 mm or higher than the peel strength of the light-transmitting film with respect to the photoreactive material layer. More preferably, the height is 3N / 50 mm or more. The upper limit value of the peeling force is not particularly limited, but is preferably 2N / 50 mm or less.

  The photoreactive material layer-containing sheet of the present invention includes a peeling force with respect to a photoreactive material layer of a light-transmitting film laminated on one surface of the photoreactive material layer, and a photoreacted material of a support laminated on the other surface. When the peeling force with respect to the layer is in the above range, the photoreactive material layer is not peeled from the support when the light transmissive film is peeled from the photoreactive material layer, and the support and the photoreactive material layer. The light-transmitting film can be easily peeled off from the photoreactant layer while maintaining a close contact state, and the workability is good.

(1) Light-transmitting film The light-transmitting film used in the present invention may be one having a release agent layer formed on at least one side of the base film, and the release agent layer is formed only on one side of the base film. Even if it is made, a release agent layer may be formed on both surfaces of the base film.

（式中、ｎは、２〜１０の整数である）
で示される官能基を有するポリオルガノシロキサン、及び、分子中に官能基としてヒドロシリル基を有するポリオルガノシロキサン架橋剤を含有する、付加型シリコーン系剥離剤組成物から形成されたものである。 The release agent layer has a general formula (1):

(In the formula, n is an integer of 2 to 10)
And a polyorganosiloxane having a functional group, and a polyorganosiloxane cross-linking agent having a hydrosilyl group as a functional group in the molecule.

  The addition-type silicone release agent composition used in the present invention comprises a polyorganosiloxane containing a functional group represented by the general formula (1) in the molecule, and a polyorgano containing a hydrosilyl group as a functional group in the molecule. It is a composition containing a siloxane cross-linking agent, and can be cured by addition reaction type cross-linking (curing reaction) by heat to form a releasable film and to exhibit useful release characteristics.

  The polyorganosiloxane containing the functional group represented by the general formula (1) preferably has an average of two or more functional groups represented by the general formula (1) in the molecule. In addition, the functional group represented by the general formula (1) is usually bonded to a silicon atom (for example, a terminal silicon atom or a silicon atom inside the main chain) of a polyorganosiloxane forming a main chain or a skeleton. Are connected.

  Examples of the functional group represented by the general formula (1) include 3-butenyl group, 4-pentenyl group, 5-hexenyl group, 6-heptenyl group, 7-octenyl group, 8-nonenyl group, 9-decenyl group, 10- An undecenyl group, 11-dodecenyl group, etc. can be mentioned. Among these, a 5-hexenyl group is preferable from the viewpoint of peeling force with respect to the photoreactive material layer.

  Examples of the polyorganosiloxane that forms the main chain or skeleton include, for example, polyalkylalkylsiloxanes such as polydimethylsiloxane, polydiethylsiloxane, and polymethylethylsiloxane; Examples thereof include a copolymer (for example, poly (dimethylsiloxane-diethylsiloxane)) in which a plurality of monomer components are used. Among these, polydimethylsiloxane is preferable. Specifically, polydimethylsiloxane having a functional group represented by the general formula (1) is preferable.

(式中、Ｒ^１〜Ｒ^３は、それぞれ独立して、一般式（１）で示される官能基又はメチル基であり、Ｒ^１〜Ｒ^３の少なくとも１つは一般式（１）で示される官能基であり、ａ＋ｂ＝１００〜８０００、ｂ／ａ＝０〜０．０５である。) Examples of the polydimethylsiloxane having a functional group represented by the general formula (1) include those represented by the following formula.

(In the formula, R ^{1 to} R ³ are each independently a functional group or a methyl group represented by the general formula (1), and at least one of R ^{1 to} R ³ is represented by the general formula (1). (It is a functional group, and a + b = 100 to 8000 and b / a = 0 to 0.05.)

In the above formula, the segment represented by (CH ₃ CH ₃ SiO) _a (CH ₃ R ² SiO) _b is a combination of a block segment of (CH ₃ CH ₃ SiO) and a block segment of (CH ₃ R ² SiO). It may be a segment, or a segment in which both are randomly combined.

  The polyorganosiloxane crosslinking agent containing a hydrosilyl group as a functional group in the molecule is a polyorgano having a hydrogen atom bonded to a silicon atom (particularly a silicon atom having a Si-H bond) in the molecule. Polyorganosiloxane which is siloxane and has 2 or more silicon atoms having Si—H bond in the molecule is particularly preferable. The silicon atom having the Si—H bond is usually bonded to a silicon atom (for example, a terminal silicon atom or a silicon atom inside the main chain) of a polyorganosiloxane forming a main chain or a skeleton. . The number of silicon atoms in the Si—H bond is not particularly limited as long as it is 2 or more. Specific examples of the polyorganosiloxane crosslinking agent containing a hydrosilyl group as a functional group in the molecule include polymethylhydrogensiloxane, poly (dimethylsiloxane-methylhydrogensiloxane), and hydrosilyl group-terminated polydimethylsiloxane. Is preferred.

(式中、Ｒ^４〜Ｒ^６は、それぞれ独立して、水素原子又はメチル基であり、Ｒ^４〜Ｒ^６の少なくとも２つは水素原子であり、ｃは１０〜１００である。) Examples of the polyorganosiloxane crosslinking agent having a hydrosilyl group include those represented by the following formula.

(Wherein R ^{4 to} R ⁶ are each independently a hydrogen atom or a methyl group, at least two of R ^{4 to} R ⁶ are hydrogen atoms, and c is 10 to 100.)

  The addition-type silicone release agent composition used in the present invention includes a polyorganosiloxane having a functional group represented by the general formula (1) in the molecule and a polyorganosiloxane cross-linking having a hydrosilyl group as a functional group in the molecule. In addition to the agent, a reaction inhibitor is preferably contained.

  The reaction inhibitor is a component used for imparting storage stability after adding a platinum-based catalyst to an addition-type silicone release agent composition. Specifically, for example, 3,5-dimethyl- Examples include 1-hexyn-3-ol, 3-methyl-1-penten-3-ol, 3-methyl-3-penten-1-in, and 3,5-dimethyl-3-hexen-1-in. The content of the reaction inhibitor is not particularly limited and can be appropriately determined.

  In addition to the above components, the addition-type silicone release agent composition used in the present invention includes a release control agent such as MQ resin, a polyorganosiloxane having no alkenyl group or hydrosilyl group (trimethyl). An adhesion improver such as a siloxy group-end-capped polydimethylsiloxane) or a polyorganosiloxane having an epoxy group may be added. Although content of these components is not specifically limited, It is 1-30 mass% with respect to the total solid in the addition-type silicone type release agent composition containing the functional group shown by General formula (1). Is preferred.

  The addition-type silicone release agent composition used in the present invention includes a polyorganosiloxane having a functional group represented by the general formula (1) in a molecule and a polyorganosiloxane crosslinking agent having a hydrosilyl group as a functional group in the molecule. And a catalyst for the curing reaction can be added. The catalyst is preferably a platinum-based catalyst.

  The platinum-based catalyst is not particularly limited, and a platinum-based catalyst generally used as a catalyst for thermosetting addition type silicone can be used. For example, chloroplatinic acid, platinum olefin complex At least one platinum-based catalyst selected from chloroplatinic acid olefin complexes is preferred, platinum olefin complexes containing siloxane structural moieties are more preferred, and Karstedt catalysts (see US Pat. Nos. 3,715,334 and 3,775,452). ) Is particularly preferred from the viewpoint of excellent silicone curability.

  The platinum-based catalyst content (concentration as platinum element) is not particularly limited, but is generally 10 to 1000 ppm (mass in terms of platinum) with respect to the total solid content of the addition-type silicone release agent composition. ppm), preferably 50 to 800 ppm, more preferably 100 to 600 ppm. If the content of the platinum-based catalyst is less than 10 ppm, the curability of the silicone tends to deteriorate, and if it exceeds 1000 ppm, the pot life of the addition-type silicone-based release agent composition tends to be shortened, and the platinum-based catalyst is expensive. Therefore, it tends to be disadvantageous in terms of cost.

  An organic solvent may be added to the addition-type silicone release agent composition used in the present invention. The organic solvent is not particularly limited. For example, hydrocarbon solvents such as cyclohexane, normal hexane, and normal heptane; aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and methyl acetate. Ketone solvents such as acetone and methyl ethyl ketone; alcohol solvents such as methanol, ethanol and butanol can be used. These organic solvents may be used alone or in combination of two or more. Although it does not specifically limit as the addition amount of an organic solvent, It is preferable that it is about 90-99.9 mass% in an addition type silicone type release agent composition.

  Various additive components (additives) may be further used in the addition-type silicone release agent composition used in the present invention, if necessary. Although it does not specifically limit as an additive component used as needed, For example, a filler, an antistatic agent, antioxidant, a ultraviolet absorber, a plasticizer, a coloring agent (dye, pigment, etc.) etc. are illustrated. These various additive components can be added within a range that does not impair the effects of the present invention. For example, it is preferably 10% by mass or less based on the total solid content in the addition-type silicone release agent composition. .

  The release agent layer can be formed by applying the addition-type silicone release agent composition to a base film described later and drying it.

  The base film may be any film having light transparency, and a plastic film having a smooth surface and high transparency is preferable. Examples of the plastic film include polyester films such as polyethylene terephthalate film and polybutylene terephthalate film; polyolefin films such as polyethylene film and polypropylene film. Also, papers that transmit ultraviolet light can be used as the base film. The surface of the base film on which the release agent layer is provided may be subjected to a treatment such as a corona treatment, a plasma treatment, or a flame treatment in advance.

  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 for the light transmissive film, the thickness is usually about 12 to 250 μm, preferably 16 to 200 μm, and more preferably 25 to 125 μm.

  The application method of the addition-type silicone release agent composition to the substrate film is not particularly limited, and any known method such as a kiss roll coater, a pea coater, a rod coater, a Meyer bar coater, a die coater, or a gravure coater. Etc. can be used. There is no particular limitation on the drying method, and any known method can be used, but a general drying method includes hot air drying. The hot air drying conditions may vary depending on the heat resistance of the base film, but are usually about 80 to 150 ° C. and preferably about 10 seconds to 5 minutes.

  The thickness of the release agent layer after drying is preferably about 30 to 500 nm, more preferably about 40 to 400 nm, and further preferably about 50 to 300 nm. When the thickness of the release agent layer is less than 30 nm, the peelability of the light transmissive film may be too high. Conversely, when the thickness exceeds 500 nm, the base that comes into contact when the light transmissive film is wound into a roll shape. There may be a problem that the material and the release agent layer are easily blocked, and a problem that the peeling force of the light transmissive film is increased.

  In the light transmissive film used in the present invention, another layer (intermediate layer) may exist between the release agent layer and the substrate film as long as the release agent layer is present on the outermost surface. In addition, any layer can be used as the intermediate layer as long as it has optical transparency, but in the present invention, the release agent layer is preferably formed directly on the substrate film.

(2) Photoreactive material layer The photoreactive composition for forming the photoreactive material layer used in the present invention is a photoreactive composition in which a product obtained by photoreaction exhibits tack at 23 ° C. It is preferable. Examples of such a photoreactive composition include a photopolymerizable composition for an acrylic pressure-sensitive adhesive. The “photoreaction” is typically a “photopolymerization reaction”.

  The photopolymerizable composition for the acrylic pressure-sensitive adhesive contains an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms as a main component and a monomer copolymerizable with the alkyl (meth) acrylate. Mention may be made of a composition containing a monomer component and a photopolymerization initiator. Here, the main component means that more than 50% by mass in all monomer components is contained, preferably 60% by mass or more, and more preferably 70% by mass or more. Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.

  Although the content rate of the monomer copolymerizable with the alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms in the monomer component is not particularly limited, for example, an alkyl group having 1 to 22 carbon atoms is selected. The alkyl (meth) acrylate having 70 to 100% by mass, the copolymerizable monomer is preferably 30 to 0% by mass, and the alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms is 80 to 96% by mass. %, And the copolymerizable monomer is more preferably 20 to 4% by mass. It is preferable that the blending ratio of the monomer components is within the above range because good adhesive properties can be obtained. Moreover, when using the alkyl (meth) acrylate which has multiple types of C1-C22 alkyl group, and the monomer which can be copolymerized, the total amount should just become said range.

  As the alkyl group related to the alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms, various linear, branched, or cyclic groups can be used. Examples of the alkyl (meth) acrylate having a linear alkyl group having 1 to 22 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n -Pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, n-dodecyl (Meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-pentadecyl (meth) acrylate, n-hexadecyl (meth) acrylate, n-heptadecyl (meth) acrylate, n-octadecyl (meta) ) Acrylate, n- Nadeshiru (meth) acrylate, n- eicosyl (meth) acrylate, n- heneicosyl (meth) acrylate, n- docosyl (meth) acrylate. Moreover, as an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms, isopropyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate , Isopentyl (meth) acrylate, neopentyl (meth) acrylate, isohexyl (meth) acrylate, 3-methylpentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl ( (Meth) acrylate, 2-propylheptyl (meth) acrylate, isoundecyl (meth) acrylate, isododecyl (meth) acrylate, isotridecyl (meth) acrylate, isomis Ril (meth) acrylate, isopentadecyl (meth) acrylate, isohexadecyl (meth) acrylate, isoheptadecyl (meth) acrylate, isostearyl (meth) acrylate, isononadecyl (meth) acrylate, isoheneicosyl (meth) acrylate, Examples thereof include isodocosyl (meth) acrylate. Examples of the cyclic alkyl group include cycloalkyl groups having 6 to 22 carbon atoms. Examples of the alkyl (meth) acrylate having a cycloalkyl group having 6 to 22 carbon atoms include cyclohexyl (meth) acrylate and cycloheptyl. (Meth) acrylate, cyclooctyl (meth) acrylate, cyclononyl (meth) acrylate, cyclodecyl (meth) acrylate, etc. can be mentioned. These can be used alone or in combination of two or more. Among these, an alkyl (meth) acrylate having an alkyl group having 8 to 18 carbon atoms is preferable, and 2-ethylhexyl (meth) acrylate and isostearyl (meth) acrylate are particularly preferable.

  The monomer copolymerizable with the alkyl (meth) acrylate is preferably at least one monomer selected from the group consisting of a hydroxyl group-containing monomer, a cyclic nitrogen-containing monomer, and an alicyclic structure-containing monomer.

  Moreover, as a hydroxyl group containing monomer, what has a polymerizable functional group which has unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group, and has a hydroxyl group can be especially used without a restriction | limiting. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl ( And (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and the like. These can be used individually by 1 type or in mixture of 2 or more types.

  The hydroxyl group-containing monomer is preferably 30% by mass or less, and more preferably 25% by mass or less, based on all monomer components forming the (meth) acrylic polymer.

  As the cyclic nitrogen-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a cyclic nitrogen structure can be used without particular limitation. The cyclic nitrogen structure preferably has a nitrogen atom in the cyclic structure. Examples of cyclic nitrogen-containing monomers include lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinyl Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as imidazole, vinyl oxazole and vinyl morpholine. Moreover, the (meth) acryl monomer containing heterocyclic rings, such as a morpholine ring, a piperidine ring, a pyrrolidine ring, a piperazine ring, is mentioned. Specific examples include N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like. Among the cyclic nitrogen-containing monomers, lactam vinyl monomers are preferable, and N-vinylpyrrolidone is more preferable.

  The cyclic nitrogen-containing monomer is preferably 20% by mass or less in all monomer components forming the (meth) acrylic polymer.

As the alicyclic structure-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having an alicyclic structure can be used without particular limitation. . The alicyclic structure is a cyclic hydrocarbon structure, preferably having 5 or more carbon atoms, more preferably 6 to 24 carbon atoms, still more preferably 8 to 20 carbon atoms, and particularly preferably 10 to 18 carbon atoms. Examples of the alicyclic structure-containing monomer include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, and isobornyl. (Meth) acrylate, dicyclopentanyl (meth) acrylate, and (meth) acrylic monomers such as HPMPA, TMA-2, and HCPA represented by the following formulas may be mentioned. Among these, isobornyl (meth) acrylate is preferable.

  It is preferable that an alicyclic structure containing monomer is 30 mass% or less in all the monomer components which form a (meth) acrylic-type polymer.

  Examples of the monomer copolymerizable with the alkyl (meth) acrylate include, in addition to the hydroxyl group-containing monomer, the cyclic nitrogen-containing monomer, and the alicyclic structure-containing monomer, a carboxyl group-containing monomer, a monomer having a cyclic ether group, and the like. be able to.

  As the carboxyl group-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, mesaconic acid, citraconic acid, Glutaconic acid and the like can be mentioned, and these can be used alone or in combination. These anhydrides can be used for itaconic acid and maleic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable. In addition, a carboxyl group-containing monomer can be arbitrarily used for the monomer component used for manufacture of the (meth) acrylic-type polymer used by this invention, On the other hand, it is not necessary to use a carboxyl group-containing monomer.

  It is preferable that a carboxyl group containing monomer is 10 mass% or less in all the monomer components which form a (meth) acrylic-type polymer.

  As the monomer having a cyclic ether group, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and a cyclic ether group such as an epoxy group or an oxetane group. It can be used without particular limitation. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Examples of the oxetane group-containing monomer include 3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, and 3-butyl-oxetanylmethyl (meth) acrylate. , 3-hexyl-oxetanylmethyl (meth) acrylate and the like. These can be used alone or in combination.

  It is preferable that the monomer which has a cyclic ether group is 10 mass% or less in all the monomer components which form a (meth) acrylic-type polymer.

  Other copolymerization monomers include vinyl acetate, vinyl propionate, styrene, α-methylstyrene; (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) Glycol acrylic ester monomers such as methoxypolypropylene glycol acrylate; Acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate; Monomer, amino group-containing monomer, imide group-containing monomer, vinyl ether monomer, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfur Phosphate, can also be used, such as (meth) acrylamide propanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyl sulfonic acid group-containing monomers such as sulfopropyl acid.

  Furthermore, the silane type monomer containing a silicon atom, etc. are mentioned. Examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane. , 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.

  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 benzophene Benzophenone compounds such as 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone Thioxanthone compounds such as 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-tria 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) phenylphos Phosphine compounds such as fin oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds Compounds; or titanocene compounds. These photoinitiators can be used individually by 1 type or in combination of 2 or more types.

  The addition amount of the photopolymerization initiator is usually about 0.01 to 5 parts by mass per 100 parts by mass of the monomer component containing a monomer copolymerizable with the alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms. It is preferable that it is 0.01-3 mass parts. When the addition amount of the photopolymerization initiator is less than the above range, the polymerization rate tends to be slow, which is not industrially preferable. Moreover, when there is more addition amount of a photoinitiator than the said range, there exists a tendency for a molecular weight to fall and to obtain a favorable adhesive characteristic.

  Moreover, a crosslinking agent can be mix | blended with the photopolymerizable composition for acrylic adhesives as needed. Examples of the crosslinking agent include polyfunctional monomers, and examples thereof include compounds having two or more unsaturated double bonds such as a (meth) acryloyl group and a vinyl group. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, for example. (Mono or poly) alkylene glycol di (meth) such as (mono or poly) ethylene glycol di (meth) acrylate and (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate In addition to acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, pentaerythritol di (meth) ) Esters of (meth) acrylic acid and polyhydric alcohols such as acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. And polyfunctional vinyl compounds such as divinylbenzene; compounds having a reactive unsaturated double bond such as allyl (meth) acrylate and vinyl (meth) acrylate.

  Although the addition amount of the polyfunctional monomer as a cross-linking agent varies depending on the number of functional groups, etc., 100 parts by mass of a monomer component containing a monomer copolymerizable with the alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms. It is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass. Use of a polyfunctional monomer in the above range is preferable because a polymer (acrylic pressure-sensitive adhesive) obtained by photopolymerizing the photopolymerizable composition can retain good cohesive force.

  Moreover, the (meth) acrylic-type oligomer can be contained in the photopolymerizable composition for acrylic adhesives used by this invention from a viewpoint of an adhesive force improvement. The (meth) acrylic oligomer is preferably a polymer having a Tg higher than that of the (meth) acrylic polymer and a small weight average molecular weight. Such a (meth) acrylic oligomer has the advantage of increasing the adhesive force, but may not be used in the present invention.

  The (meth) acrylic oligomer preferably has a Tg of about 0 ° C. or higher and 300 ° C. or lower, preferably about 20 ° C. or higher and 300 ° C. or lower, more preferably about 40 ° C. or higher and 300 ° C. or lower. Adhesive force can be improved when Tg is within the above range. The Tg of the (meth) acrylic oligomer is a theoretical value calculated based on the Fox equation, similar to the Tg of the (meth) acrylic polymer.

  Regarding the Tg of the homopolymer, the numerical value described in “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) is used. In addition, the highest value is employ | adopted about the monomer in which multiple types of value is described in this literature.

  When not described in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc, 1989), values obtained by the following measurement method are used (Japanese Patent Laid-Open No. 2007-51271). reference).

  Specifically, a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser was charged with 100 parts by weight of monomer, 0.2 part by weight of azobisisobutyronitrile and 200 parts by weight of ethyl acetate as a polymerization solvent. Stir for 1 hour while flowing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature is raised to 63 ° C. and the reaction is carried out for 10 hours. Next, the mixture is cooled to room temperature to obtain a homopolymer solution having a solid concentration of 33% by weight. Subsequently, this homopolymer solution is cast-coated on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. This test sample was punched out into a disk shape having a diameter of 7.9 mm, sandwiched between parallel plates, and subjected to a shear strain at a frequency of 1 Hz using a viscoelasticity tester (trade name “ARES”, manufactured by Rheometrics), while in the temperature region − Viscoelasticity is measured by a shear mode at a heating rate of 70 to 150 ° C. and 5 ° C./min, and the peak top temperature of tan δ (loss tangent) is defined as Tg of the homopolymer.

  The weight average molecular weight of the (meth) acrylic oligomer is 1000 or more and less than 30000, preferably 1500 or more and less than 20000, and more preferably 2000 or more and less than 10,000. It is preferable for the weight average molecular weight to be in the above-mentioned range since good adhesive force and holding characteristics can be obtained. In this invention, the measurement of the weight average molecular weight of a (meth) acrylic-type oligomer can be calculated | required in polystyrene conversion by GPC method. Specifically, TSKgelGMH-H (20) × 2 columns are used in HPLC 8020 manufactured by Tosoh Corporation, and measurement is performed with a tetrahydrofuran solvent at a flow rate of about 0.5 ml / min.

  Examples of the monomer constituting the (meth) acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , S-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undeci Alkyl (meth) acrylates such as (meth) acrylate and dodecyl (meth) acrylate; (meth) acrylic acid and alicyclic such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate An ester with a group alcohol; an aryl (meth) acrylate such as phenyl (meth) acrylate and benzyl (meth) acrylate; a (meth) acrylate obtained from a terpene compound derivative alcohol; and the like. Such (meth) acrylates can be used alone or in combination of two or more.

  Examples of (meth) acrylic oligomers include alkyl (meth) acrylates in which alkyl groups such as isobutyl (meth) acrylate and t-butyl (meth) acrylate have a branched structure; cyclohexyl (meth) acrylate and isobornyl (meth) Esters of (meth) acrylic acid and alicyclic alcohols such as acrylate and dicyclopentanyl (meth) acrylate; cyclic structures such as aryl (meth) acrylate such as phenyl (meth) acrylate and benzyl (meth) acrylate From the viewpoint of further improving the adhesiveness of the pressure-sensitive adhesive layer, it is preferable that the monomer unit contains an acrylic monomer having a relatively bulky structure, represented by (meth) acrylate having a viscosity. In addition, when ultraviolet rays (ultraviolet rays) are employed in the synthesis of the (meth) acrylic oligomer or in the production of the pressure-sensitive adhesive layer, those having a saturated bond are preferred in that they are less likely to cause polymerization inhibition. An alkyl (meth) acrylate having an alkyl group having a branched structure or an ester with an alicyclic alcohol can be suitably used as a monomer constituting the (meth) acrylic oligomer.

  From this point, suitable (meth) acrylic oligomers include, for example, a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA), and a copolymer of cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA). Polymer, copolymer of cyclohexyl methacrylate (CHMA) and acryloylmorpholine (ACMO), copolymer of cyclohexyl methacrylate (CHMA) and diethylacrylamide (DEAA), copolymer of 1-adamantyl acrylate (ADA) and methyl methacrylate (MMA) Polymer, copolymer of dicyclopentanyl methacrylate (DCPMA) and isobornyl methacrylate (IBXMA), dicyclopentanyl methacrylate (DCPMA) and methyl Tacrylate (MMA) copolymer, dicyclopentanyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), dicyclopentanyl acrylate (DCPA), 1 -Adamantyl methacrylate (ADMA), 1-adamantyl acrylate (ADA) homopolymers, and the like. In particular, an oligomer containing MMA as a main component is preferable, and a copolymer of dicyclopentanyl methacrylate (DCPMA) and methyl methacrylate (MMA) is more preferable.

  In the photopolymerizable composition for an acrylic pressure-sensitive adhesive used in the present invention, when the (meth) acrylic oligomer is used, the content thereof is not particularly limited, but it is 10 with respect to 100 parts by weight of the (meth) acrylic polymer. It is preferably no greater than 5 parts by weight, more preferably no greater than 5 parts by weight, and even more preferably no greater than 3 parts by weight.

  Furthermore, the photoreactive composition used in the present invention includes a viscosity modifier, a release modifier, a tackifier, a plasticizer, a softener, glass fiber, glass beads, metal powder, and other inorganic materials as necessary. Various additives such as fillers, pigments, colorants (pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, ultraviolet absorbers, etc., that do not depart from the object of the present invention. Can also be used as appropriate.

  The photoreactive material layer constituting the photoreactive material layer-containing sheet of the present invention can be formed by photoreacting the above-mentioned photoreactive composition, and the formation method thereof will be described later.

  The thickness of the photoreactive material layer is not particularly limited and can be appropriately determined according to its use. When the photoreactive material layer is an adhesive layer, the thickness is 25 to 300 μm. Is preferably about 50 to 200 μm.

  The use of the photoreactive material layer in the photoreactive material layer-containing sheet of the present invention is not particularly limited. For example, the pressure-sensitive adhesive layer as described above, a base material for an adhesive tape, It can be set as the layer, film, and sheet | seat used for various uses other than.

(3) Support The support used in the present invention may be one that transmits light or one 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 peeling treatment to the support is not particularly limited, and may be a peeling treatment in which the peeling force of the support to the photoreactive material layer is higher than that of the light transmissive film to the photoreactive material layer. That's fine. Specifically, there is a method of adjusting the peeling force by blending a solvent-soluble organopolysiloxane resin, and R ⁷ ₃ SiO _1/2 (wherein R ⁷ is a monovalent hydrocarbon group) and SiO _4/2 The method etc. which mix | blend MQ resin which consists of a siloxane unit shown by addition type silicone composition etc. can be mentioned.

Examples of commercially available MQ resins include KS-3800 and X-92-183 manufactured by Shin-Etsu Chemical Co., Ltd., SD7292 manufactured by Toray Dow Corning, BY24-843, and the like. Moreover, as a method other than blending the MQ resin, for example, a vinyl group-containing addition type silicone release agent (addition type silicone release agent having a —CH═CH ₂ group) can also be used.

  When the support is a release film that has been subjected to a release treatment, the support is preferably laminated so that the release-treated surface of the support is in contact with the photoreactive material layer.

（式中、ｎは、２〜１０の整数である）
で示される官能基を有するポリオルガノシロキサン、及び、分子中にヒドロシリル基を有するポリオルガノシロキサン架橋剤を含有する、付加型シリコーン系剥離剤組成物から形成されたものであることを特徴とするものである。 2. Method for producing photoreactive material layer-containing sheet The method for producing a photoreactive material layer-containing sheet of the present invention comprises:
The support, the coating layer formed from the photoreactive composition, and the light-transmitting film having the release agent layer on the base film are in this order, and the release agent layer of the light-transmitting film and the application A step of forming a laminate in which the layers are in contact with each other;
Irradiating the laminate with light to photoreact the coating layer formed from the photoreactive composition to form a photoreactive material layer,
In the molecule, the release agent layer has the general formula (1):

(In the formula, n is an integer of 2 to 10)
It is formed from an addition-type silicone release agent composition containing a polyorganosiloxane having a functional group represented by the formula (1) and a polyorganosiloxane crosslinking agent having a hydrosilyl group in the molecule. It is.

  The support, the photoreactive composition, and the light transmissive film are as described above.

  As a method of forming the laminate, the laminate may be laminated so that the release agent layer of the light transmissive film and the coating layer are in contact with each other, and the lamination order is not particularly limited. For example, a photoreactive composition is applied to at least one surface of a support to form a coating layer, and the light-transmitting film is disposed on the coating layer so that the release agent layer of the light-transmitting film is in contact with the coating layer. And a method of coating a photoreactive composition on a release agent layer of a light transmissive film to form a coating layer and laminating a support on the coating layer.

  The coating layer is formed by coating a photoreactive composition on a support or a release film layer of a light transmissive film. Examples of the coating method include a baker type applicator, a die coater, a roll coater, and a roll knife coater. , Known coating methods such as a lip coater, a closed edge die coater, a gravure coater, a curtain coater, and a CAP coater.

  The thickness of the coating layer is not particularly limited, and can be appropriately determined according to the thickness after photopolymerization (that is, the thickness of the photoreactive material layer). For example, when the photoreactive composition is a photopolymerizable composition for an acrylic pressure-sensitive adhesive, the thickness of the coating layer is appropriately determined so that the pressure-sensitive adhesive layer finally obtained is about 30 to 300 μm. be able to.

  The photoreactive material layer-containing sheet of the present invention can be obtained by irradiating the laminate with light, causing the coating layer formed from the photoreactive composition to photoreact to form a photoreactive material layer. it can.

  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. Examples of such light irradiation devices include LEDs, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, microwave-excited mercury lamps, black light lamps, chemical lamps, sterilization lamps, and low-pressure discharge mercury lamps Excimer lasers can be used, and one or a combination of two or more of these may be used.

  In addition, it is desirable to irradiate ultraviolet rays 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. It is preferable to perform irradiation by cutting short-wavelength light because it has an effect of suppressing heavy peeling. In addition, as will be described later, the light transmissive film may be used repeatedly, which is preferable because deterioration of the light transmissive film can be suppressed. 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.

  Moreover, the said light irradiation may be performed continuously and may be performed intermittently.

When the photoreactive composition is a photopolymerizable composition, the light irradiation intensity of the photoreactive composition coating layer by the ultraviolet irradiation lamp is a factor that determines the degree of polymerization of the resulting polymer. Specifically, the illuminance of ultraviolet rays is preferably 0.1~300mW / cm ^2, more preferably 1~50mW / cm ^2. When the illuminance is lower than the above range, the polymerization reaction time becomes long and the productivity tends to be inferior. Moreover, since photoinitiator will be consumed rapidly when illumination intensity is higher than the said range, there exists a tendency for the molecular weight reduction of a polymer to occur.

Further, the irradiation light amount of ultraviolet rays is preferably about 100 to 600 mJ / cm ² · min, and preferably about 200 to 500 mJ / cm ² · min. Moreover, although irradiation time can be suitably determined with the illumination intensity and irradiation light quantity of an ultraviolet-ray, it is about 10 second-about 10 minutes normally.

  The light irradiation to the laminate is preferably performed from the light transmissive film side. In addition, when the support is light transmissive, the light may be irradiated from the support side instead of being irradiated from the light transmissive film side, or the light irradiation may be performed from both the light transmissive film side and the support side. You may go.

  Moreover, in the production method of the present invention, the laminate is irradiated with light to form a photoreactive material layer, and a photoreactive material layer-containing sheet is formed.From the obtained photoreactive material layer-containing sheet, The light transmissive film is peeled off, and another release film can be laminated on the photoreactant layer to form a photoreactor layer-containing sheet. The release film used in this case is not particularly limited, and a known release film can be suitably used. Moreover, the peeled light transmissive film can be used again in the production method of the present invention.

  In the production method of the present invention, when the coating layer formed from the photoreactive composition is irradiated with light, a light-transmitting film that has been subjected to a release treatment with a specific release agent is present on the coating layer. Unreacted components in the photoreactive composition such as a reactive monomer are not scattered and contamination of the light irradiation means can be prevented. Further, since the contamination of the light irradiation means is prevented, it is possible to prevent a decrease in the illuminance of light. Moreover, when peeling a light transmissive film from a photoreactive material layer containing sheet | seat, only a light transmissive film peels in the state in which the photoreactive material layer was closely_contact | adhered to the support body.

  EXAMPLES 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.

Production Example 1 (Preparation of photoreactive composition)
2-ethylhexyl acrylate (2EHA) 40.5 parts by mass, isostearyl acrylate (ISA) 40.5 parts by mass, 4-hydroxybutyl acrylate (4HBA) 1 part by mass, N-vinyl-2-pyrrolidone (NVP) 18 A syrup partially photopolymerized by adding 0.05 parts by mass of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator to 4 parts by weight in a flask and exposing to ultraviolet rays in a nitrogen atmosphere. Got. To 100 parts by mass of this partially polymerized syrup, 0.3 part by mass of trimethylolpropane triacrylate as a crosslinking agent was uniformly mixed to obtain an acrylic pressure-sensitive adhesive (1) (photoreactive composition).

Production Example 2 (Preparation of photoreactive composition)
2-ethylhexyl acrylate (2EHA) 28.5 parts by mass, isostearyl acrylate (ISA) 28.5 parts by mass, 4-hydroxybutyl acrylate (4HBA) 21 parts by mass, isobornyl acrylate (IBXA) 22 parts by mass As a photopolymerization initiator, 0.05 parts by mass of 2,2-dimethoxy-2-phenylacetophenone was added to 4 flasks and exposed to ultraviolet rays in a nitrogen atmosphere to obtain a partially photopolymerized syrup. . To 100 parts by mass of this partially polymerized syrup, 0.3 part by mass of trimethylolpropane triacrylate as a crosslinking agent was uniformly mixed to obtain an acrylic pressure-sensitive adhesive (2) (photoreactive composition).

Production Example 3 (Preparation of photoreactive composition)
As a photopolymerization initiator, 78 parts by mass of 2-ethylhexyl acrylate (2EHA), 21.6 parts by mass of 2-hydroxyethyl acrylate (HEA), 18 parts by mass of N-vinyl-2-pyrrolidone (NVP), 0.05 parts by mass of 2-dimethoxy-2-phenylacetophenone was added to 4 flasks and exposed to ultraviolet rays in a nitrogen atmosphere to obtain a partially photopolymerized syrup. To 100 parts by mass of this partially polymerized syrup, 0.3 part by mass of trimethylolpropane triacrylate as a crosslinking agent was uniformly mixed to obtain an acrylic pressure-sensitive adhesive (3) (photoreactive composition).

Production Example 4 (Preparation of addition-type silicone release agent composition)
Hexenyl group-containing addition type silicone (trade name: LTC300B, 30% toluene solution, manufactured by Toray Dow Corning) 100 parts by weight, platinum catalyst (trade name: SRX212, manufactured by Toray Dow Corning) 1 part by weight, as dilution solvent 1,500 parts by mass of toluene and 1500 parts by mass of normal hexane were mixed to produce an addition-type silicone release agent composition (1).

Production Examples 5 to 9 (Preparation of addition-type silicone release agent composition)
Addition type silicone release agent compositions (2) to (6) were produced in the same manner as in Production Example 4 except that the compositions shown in Table 1 were used.

Abbreviations in Table 1 are as follows.
LTC300B: Addition type silicone containing hexenyl group (addition type silicone release agent containing polyorganosiloxane having hexenyl group in molecule and polyorganosiloxane crosslinking agent having hydrosilyl group in molecule, 30% toluene solution, (Toray Dow Corning)
LTC761: Addition type silicone containing hexenyl group (addition type silicone release agent containing polyorganosiloxane having hexenyl group in molecule and polyorganosiloxane crosslinker having hydrosilyl group in molecule, 30% toluene solution, (Toray Dow Corning)
SRX211: Additive silicone containing vinyl group (30% toluene solution, manufactured by Toray Dow Corning)
KS-847T: Addition type vinyl group-containing silicone (30% toluene solution, manufactured by Shin-Etsu Chemical Co., Ltd.)
X-62-2829: Addition type vinyl group-containing silicone (30% toluene solution, manufactured by Shin-Etsu Chemical Co., Ltd.)
SRX212: Platinum catalyst (Toray Dow Corning)
CAT-PL-50T: Platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd.)

Example 1
(Preparation of a light-transmitting film subjected to release treatment)
Using Mayer Bar # 6, the addition-type silicone release agent composition (1) produced in Production Example 4 is applied to a polyester film (base film, trade name: Lumirror S-10, manufactured by Toray Industries, Inc.) having a thickness of 50 μm. After coating, the film was heated with a hot air dryer at 130 ° C. for 1 minute to produce a light transmissive film having a release agent layer (coating amount: 0.07 g / m ² , thickness: 70 nm).

(Production of support)
92 parts by mass of vinyl group-containing silicone release agent (trade name: KS-3703, manufactured by Shin-Etsu Chemical Co., Ltd.), 8 parts by mass of silicon control agent (trade name: KS-3800, manufactured by Shin-Etsu Chemical Co., Ltd.), platinum 3 parts by mass of a catalyst (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.), 680 parts by mass of toluene as a diluent solvent, and 680 parts by mass of normal hexane are mixed, and a release agent solution for support (1) Adjusted. Using the Mayer bar # 6, the prepared release agent solution for support (1) was applied to a 50 μm thick polyester film (base film, trade name: Lumirror S-10, manufactured by Toray Industries, Inc.) and then dried with hot air The support (1) having a release agent layer (coating amount: 0.1 g / m ² ) was prepared by heating at 130 ° C. for 1 minute using a machine.

(Preparation of photoreactive material layer-containing sheet)
The thickness of the acrylic pressure-sensitive adhesive layer (photoreaction product layer) after photoreaction was determined using the Baker-type applicator on the release layer surface of the light-transmitting film. A coating layer was formed by coating to 100 μm. A sample was prepared by bonding the support (1) onto the coating layer so that the release agent layer on the support (1) was in contact with the coating layer. From the light transmissive film side of the sample, a black light was irradiated at an illuminance of 5 mW / cm ² and a light amount of 300 mJ / cm ² · min for 3 minutes to carry out a photoreaction, thereby producing a photoreactive material layer-containing sheet.

Example 2
In Example 1 (Preparation of release-processed light-transmitting film), in place of addition-type silicone release agent composition (1), addition-type silicone release agent composition (2) produced in Production Example 5 A photoreactant layer-containing sheet was produced in the same manner as in Example 1 except that was used.

Example 3
In Example 1 (Preparation of release-processed light-transmitting film), in place of addition-type silicone release agent composition (1), addition-type silicone release agent composition (3) produced in Production Example 6 In Example 1 (production of a photoreactive material layer-containing sheet), the acrylic pressure-sensitive adhesive (2) obtained in Production Example 2 was used in place of the acrylic pressure-sensitive adhesive (1), and light was used. A photoreactive material layer-containing sheet was prepared in the same manner as in Example 1 except that the coating layer was formed so that the thickness of the acrylic pressure-sensitive adhesive layer after the reaction was 50 μm.

Example 4
In Example 3 (production of a photoreactive material layer-containing sheet), light was applied in the same manner as in Example 3 except that the coating layer was formed so that the thickness of the acrylic pressure-sensitive adhesive layer after photoreaction was 75 μm. A reactant layer-containing sheet was prepared.

Example 5
In Example 3 (production of a photoreactive material layer-containing sheet), light was applied in the same manner as in Example 3 except that the coating layer was formed so that the thickness of the acrylic pressure-sensitive adhesive layer after photoreaction was 100 μm. A reactant layer-containing sheet was prepared.

Example 6
In Example 5 (production of a photoreactive material layer-containing sheet), a photoreactant was obtained in the same manner as in Example 5 except that the acrylic pressure-sensitive adhesive (3) was used instead of the acrylic pressure-sensitive adhesive (2). A layer-containing sheet was prepared.

Example 7
(Preparation of a light-transmitting film subjected to release treatment)
Using Mayer Bar # 6, the addition-type silicone release agent composition (1) produced in Production Example 4 is applied to a polyester film (base film, trade name: Lumirror S-10, manufactured by Toray Industries, Inc.) having a thickness of 50 μm. After coating, the film was heated with a hot air dryer at 130 ° C. for 1 minute to produce a light transmissive film having a release agent layer (coating amount: 0.07 g / m ² , thickness: 70 nm).

(Production of support)
100 parts by mass of vinyl group-containing silicone release agent (trade name: KS-847H, 30% toluene solution, manufactured by Shin-Etsu Chemical Co., Ltd.), platinum catalyst (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) ) 1 part by mass, 1100 parts by mass of toluene as a dilution solvent, and 1100 parts by mass of normal hexane were mixed to prepare a release agent solution for support (2). Using the Mayer bar # 6, the prepared release agent solution for support (2) was applied to a 75 μm thick polyester film (base film, trade name: Lumirror S-10, manufactured by Toray Industries, Inc.) and then dried with hot air was heated 130 ° C. × 1 minute machine, release agent layer (coating amount: 0.1 g / ^{m 2)} was prepared support having a (2).

(Preparation of photoreactive material layer-containing sheet)
The acrylic pressure-sensitive adhesive (1) obtained in Production Example 1 was applied to the release layer surface of the light-transmitting film using a baker-type applicator so that the thickness of the krill-based pressure-sensitive adhesive layer after photoreaction was 100 μm. Thus, a coating layer was formed. A sample was prepared by bonding the support (2) onto the coating layer so that the release agent layer on the support (2) was in contact with the coating layer. From the light transmissive film side of the sample, a black light was irradiated at an illuminance of 5 mW / cm ² and a light amount of 300 mJ / cm ² · min for 3 minutes to carry out a photoreaction to produce a photoreactive material layer-containing sheet.

Example 8
In Example 7 (preparation of support), a 75 μm thick polyester film (base film, trade name: Lumirror S-10, manufactured by Toray Industries, Inc.) and a 50 μm thick polyester film (base film, trade name) : Lumirror S-10, manufactured by Toray Industries, Inc., a photoreactive material layer-containing sheet was produced in the same manner as in Example 7.

Comparative Examples 1-3
In Example 1 (production of a light-transmitting film subjected to a release treatment), instead of the addition-type silicone release agent composition (1), the addition-type silicone release agent composition produced in Production Examples 7 to 9 ( A photoreactive material layer-containing sheet was produced in the same manner as in Example 1 except that 4) to (6) were used.

  The following evaluation was performed about the photoreaction material layer containing sheet | seat obtained by the said Example and the comparative example. The evaluation results are shown in Table 2.

<Peeling power of light transmissive film to photoreactive material layer>
The photoreactive material layer-containing sheets obtained in Examples and Comparative Examples were cut out to a width of 50 mm, stored for 0.5 hours at 23 ° C. after irradiation with black light, and then lighted from the photoreactive material layer-containing sheets using a tensile tester. The peeling force when peeling the permeable film was measured. The peeling conditions are as follows.
(Peeling condition)
Peel angle: 180 °
Tensile speed: 0.3 m / min
Measurement temperature: 23 ° C

<Peeling strength of support to photoreactive material layer>
Except that the support was peeled from the photoreactive material layer-containing sheet, the peeling force was measured by the same method as in the above <Peeling force of light transmissive film to photoreactive material layer>.

  In the photoreactive material layer-containing sheets obtained in the examples, the peel strength of the support to the photoreactive material layer is higher than the peel strength of the light transmissive film to the photoreactive material layer, and the photoreaction of the light transmissive film. Since the peeling force with respect to the physical layer was 0.5 N / 50 mm or less, the light-transmitting film could be easily peeled from the photoreactive material layer without peeling the photoreactive material layer from the support. Moreover, in the photoreactive material layer-containing sheet obtained in the examples, the photoreactive material layer was not deformed when the light transmissive film was peeled off.

DESCRIPTION OF SYMBOLS 1 Photoreactive material layer containing sheet 2 Base film 3 Release agent layer 4 Light transmissive film 5 Photoreactive material layer 6 Support body

Claims (11)

A release film subjected to a release treatment , a photoreactive material layer obtained by photoreacting the photoreactive composition, and a light-transmitting film having a release agent layer on the base film are bonded together in this order, and The release-treated surface of the release film subjected to the release treatment is in contact with the photoreactive material layer, and the release agent layer of the light-transmitting film is in contact with the photoreactive material layer. Because
In the molecule, the release agent layer has the general formula (1):

(In the formula, n is an integer of 2 to 10)
Formed from an addition-type silicone release agent composition containing a polyorganosiloxane having a functional group represented by the formula (1) and a polyorganosiloxane crosslinking agent having a hydrosilyl group in the molecule,
The peeling force with respect to the photoreactive material layer of the light transmissive film is 0.5 N / 50 mm or less,
Peel strength with respect to the light reaction product layer of release film is the release treatment, being higher than the release force to light reaction product layer of the light transmissive film, the light reaction layer containing sheet.   The photoreactive material layer-containing sheet according to claim 1, 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 adhesive comprises a monomer component containing an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and a monomer copolymerizable with the alkyl (meth) acrylate, and a photopolymerization initiator It is a photopolymerizable composition for acrylic pressure-sensitive adhesives containing   The monomer component contains 70% by mass or more of an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and 30% by mass or less of a copolymerizable monomer. Photoreactive substance layer-containing sheet.   The photoreactant layer-containing sheet according to any one of claims 1 to 4, wherein the base film is a polyester film. The release film subjected to the release treatment, the coating layer formed from the photoreactive composition, and the light transmissive film having the release agent layer on the base film are in this order, and the release film subjected to the release treatment. A step of forming a laminate in which the release treatment surface is in contact with the coating layer and the release layer of the light-transmitting film and the coating layer are in contact with each other;
Irradiating the laminate with light to photoreact the coating layer formed from the photoreactive composition to form a photoreactive material layer,
In the molecule, the release agent layer has the general formula (1):

(In the formula, n is an integer of 2 to 10)
Formed from an addition-type silicone release agent composition containing a polyorganosiloxane having a functional group represented by the formula (1) and a polyorganosiloxane crosslinking agent having a hydrosilyl group in the molecule,
A method for producing a photoreactive material layer-containing sheet, wherein the support (excluding the polarizing plate) has a higher peeling force with respect to the photoreactive material layer than that of the light transmissive film with respect to the photoreactive material layer. . The said photoreactive composition is a photopolymerizable composition for adhesives, and the said photoreaction material layer is an adhesive layer, The manufacturing method of the photoreaction material layer containing sheet | seat of Claim 6 characterized by the above-mentioned. . The photopolymerizable composition for pressure-sensitive adhesive comprises a monomer component containing an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and a monomer copolymerizable with the alkyl (meth) acrylate, and a photopolymerization initiator The method for producing a photoreacted material layer-containing sheet according to claim 7 , wherein the photopolymerizable composition for an acrylic pressure-sensitive adhesive contains a photoreactive material layer-containing sheet. The monomer component, an alkyl having an alkyl group of 1 to 22 carbon atoms (meth) acrylate of 70 wt% or more, and, characterized in that it comprises a copolymerizable monomer than 30 weight%, according to claim 8 The manufacturing method of the photoreaction material layer containing sheet | seat. The method for producing a photoreactive material layer-containing sheet according to any one of claims 6 to 9 , wherein the base film is a polyester film. The photoreaction material layer containing sheet manufactured with the manufacturing method of any one of Claims 6-10 .

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