JP7215061B2 - Block copolymer, surface conditioner, adhesive composition, adhesive sheet, adhesive protective sheet, laminate, optical member and electronic member - Google Patents

Description

The present disclosure relates to block copolymers, surface conditioners, adhesive compositions, adhesive sheets, adhesive protective sheets, laminates, optical members, and electronic members.

For example, in the manufacturing process of flexible printed circuit boards and printed circuit boards, the board may be damaged, contaminated with chemicals, and deteriorated due to chemicals used during the manufacturing process or heating during the manufacturing process. Therefore, in order to prevent the above-described damage, contamination, deterioration, etc. in the manufacturing process of the substrate, a technique using a protective sheet for protecting the surface of the substrate has been proposed (for example, Patent Document 1).

Such a protective sheet has, for example, a substrate and an adhesive layer arranged on one side of the substrate. Also, the protective sheet is a member that is finally peeled off from the product that is the member to be protected. Therefore, it is preferable to use an adhesive layer for the protective sheet, which has a characteristic that the protective sheet can be peeled off from the member to be protected.
However, in recent years, various products have been used as members to be protected. When peeling, the force required to peel the protective sheet from the member to be protected increases, and there is a new problem that the protective sheet cannot be easily peeled from the member to be protected.
In addition, due to the increasing precision and complexity of various electronic components, the thickness of the protected component itself, the integration of functions, and the miniaturization of the component itself are likely to break the protected component itself and the surface of the protected component. In addition, when the protective sheet is removed, it is required to peel off easily with less load on the member to be protected.

On the other hand, in Patent Documents 2 to 4, by using a block copolymer containing an organopolysiloxane structure in the main chain or a graft copolymer containing an organopolysiloxane structure in the side chain, water and oil repellency is improved. , releasability, antifouling property, slipperiness and the like are described.
Conventional block copolymers containing organopolysiloxane in the main chain are those in which organopolysiloxane is introduced in blocks at the terminal portion of the main chain by using an organopolysiloxane-based high-molecular-weight azo initiator. be. In addition, a conventional graft copolymer containing an organopolysiloxane structure in a side chain is obtained by randomly copolymerizing an organopolysiloxane compound having a radically polymerizable group and a radically polymerizable monomer at the same time. A graft copolymer is obtained.

JP-A-2017-8173 JP-A-2000-309673 JP 2007-291372 A JP 2016-79301 A

Conventional adhesive protective sheets can be easily peeled off from the member to be protected when the force required to peel the protective sheet from the member to be protected increases, such as when the surface to which the protective sheet is attached has a large area. However, when the protected member itself or the surface of the protected member is likely to break, the load on the protected member is high, and the easy peelability from the protected member is still insufficient.
There has been a demand for an adhesive protective sheet or adhesive sheet having an adhesive layer that can be easily peeled off from a member to be protected so as to reduce the load on the member to be protected.
Therefore, there has been a demand for a polymer or surface conditioner containing an organopolysiloxane structure that can improve the effect of imparting peelability and the like to the surface.

The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a polymer or surface conditioner containing an organopolysiloxane structure, which can improve the effect of imparting peelability and the like to the surface. .
In addition, the present disclosure is an adhesive that can form an adhesive layer that has sufficient adhesive strength when used, can reduce the peeling force from the adherend when peeled, and has excellent easy peelability from the adherend. An object of the present invention is to provide a composition, a pressure-sensitive adhesive sheet that uses the pressure-sensitive adhesive composition and is excellent in easy peelability from an adherend, an adhesive protective sheet, a laminate, an optical member, and an electronic member using the pressure-sensitive adhesive sheet. do.

One embodiment of the present disclosure is a block copolymer having an A block containing a structural unit represented by the following general formula (I) and a B block containing a structural unit represented by the following general formula (II): offer.

（一般式（Ｉ）中、Ｒ^１は、水素原子又はメチル基、Ｒ^２は、置換基を有していても良く、炭素鎖中に酸素原子が含まれていても良い１価の炭化水素基を表し、
一般式（ＩＩ）中、Ｒ^３は、水素原子又はメチル基、Ｌ^１は、－ＣＯＯ－、－ＯＣＯ－、－Ｏ－、－ＣＯＮＨ－、－ＣＯＳ－、又は直接結合、Ｌ^２は、－Ｏ－、－ＮＨ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＯＮＨ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＮＨＣＯＮＨ－、及び－Ｓｉ（Ｒ^Ｌａ）（Ｒ^Ｌｂ）－からなる群から選択される１種以上が含まれていても良く、水酸基で置換されていても良い炭素数１～１５の炭化水素基を含む２価の基、又は直接結合、Ｒ^４～Ｒ^８は、それぞれ独立に、炭素数１～２０の置換基を有していても良い１価の炭化水素基、水素原子、水酸基、炭素数１～２０のアルコキシ基、又は下記一般式（ＩＩＩ）で表される基を表し、Ｒ^Ｌａ及びＲ^Ｌｂは、それぞれ独立に、炭素数１～２０の置換基を有していても良い１価の炭化水素基、水素原子、水酸基、又は炭素数１～２０のアルコキシ基を表し、ａは１～５０の整数である。）

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is a monovalent hydrocarbon which may have a substituent and which may contain an oxygen atom in the carbon chain. represents the group,
In general formula (II), R ³ is a hydrogen atom or a methyl group, L ¹ is -COO-, -OCO-, -O-, -CONH-, -COS-, or a direct bond, and L ² is - the group consisting of O-, -NH-, -S-, -COO-, -OCO-, -OCONH-, -NHCO-, -CONH-, -NHCONH-, and -Si(R ^La )(R ^Lb )- a divalent group containing a hydrocarbon group having ¹ to ¹⁵ carbon atoms which may be substituted with a hydroxyl group, or a direct bond; Each independently, a monovalent hydrocarbon group optionally having a substituent of 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or represented by the following general formula (III) R ^La and R ^Lb are each independently a monovalent hydrocarbon group optionally having a substituent of 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, or a represents an alkoxy group, and a is an integer of 1-50. )

（一般式（ＩＩＩ）中、Ｒ^９～Ｒ^１３は、それぞれ独立に、炭素数１～２０の置換基を有していても良い１価の炭化水素基、水素原子、水酸基、又は炭素数１～２０のアルコキシ基を表し、ｂは０～５０の整数である。）

(In general formula (III), R ⁹ to R ¹³ are each independently a monovalent hydrocarbon group optionally having a substituent of 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, or a represents an alkoxy group of ~20, and b is an integer of 0 to 50.)

One embodiment of the present disclosure is the block copolymer, wherein the A block contains a monomer-derived structural unit containing one or more selected from the group consisting of a hydroxyl group, an epoxy group, a carboxy group, and an amino group. I will provide a.

One embodiment of the present disclosure provides a surface modifier that is the block copolymer of one embodiment of the present disclosure.

One embodiment of the present disclosure is an adhesive containing an energy ray-curable component containing a (meth)acrylic acid ester polymer, an energy ray initiator, and the block copolymer of one embodiment of the present disclosure. A composition is provided.

One embodiment of the present disclosure provides an adhesive composition that further contains a thermal cross-linking agent in addition to the adhesive composition.
Moreover, one embodiment of the present disclosure provides an adhesive composition, wherein the thermal cross-linking agent is an isocyanate-based cross-linking agent.

One embodiment of the present disclosure has an adhesive layer and a substrate disposed on one side of the adhesive layer,
Provide a pressure-sensitive adhesive sheet, wherein the pressure-sensitive adhesive layer has a characteristic that the pressure-sensitive adhesive strength decreases from the initial pressure-sensitive adhesive strength due to energy ray irradiation, and the pressure-sensitive adhesive layer is a cured product of the pressure-sensitive adhesive composition of the embodiment of the present disclosure. .

One embodiment of the present disclosure provides an adhesive protective sheet, which is the adhesive sheet of one embodiment of the present disclosure.

An embodiment of the present disclosure provides a laminate of the adhesive protective sheet of the embodiment of the present disclosure and a member to be protected attached to the adhesive layer side of the adhesive protective sheet.

An embodiment of the present disclosure provides an optical member to which the adhesive protective sheet of the embodiment of the present disclosure is adhered.
Moreover, one embodiment of the present disclosure provides an electronic member to which the adhesive protective sheet of the one embodiment of the present disclosure is adhered.

According to the embodiments of the present disclosure, it is possible to provide a polymer or surface conditioner containing an organopolysiloxane structure that can improve the effect of imparting peelability and the like to the surface.
In addition, the present disclosure is an adhesive that can form an adhesive layer that has sufficient adhesive strength when used, can reduce the peeling force from the adherend when peeled, and has excellent easy peelability from the adherend. It is possible to provide a composition, a pressure-sensitive adhesive sheet excellent in easy peelability from an adherend using the pressure-sensitive adhesive composition, an adhesive protective sheet, a laminate, an optical member, and an electronic member using the pressure-sensitive adhesive sheet.

1 is a schematic cross-sectional view of an example of a pressure-sensitive adhesive sheet according to an embodiment of the present disclosure; FIG. 1 is a schematic cross-sectional view of an example of a laminate according to an embodiment of the present disclosure; FIG.

Hereinafter, embodiments, examples, and the like of the present disclosure will be described with reference to the drawings and the like. However, the present disclosure can be implemented in many different aspects, and should not be construed as being limited to the descriptions of the embodiments, examples, and the like exemplified below. In addition, in order to make the description clearer, the drawings may schematically show the width, thickness, shape, etc. of each part compared to the actual embodiment, but this is only an example, and the interpretation of the present disclosure is not intended. It is not limited. In addition, in this specification and each figure, the same reference numerals may be given to the same elements as those described above with respect to the existing figures, and detailed description thereof may be omitted as appropriate. Also, for convenience of explanation, the terms "upper" and "lower" may be used, but the up-down direction may be reversed.
“In this specification, when a configuration, such as a member or a region, is “above (or below)” another configuration, such as another member or region, unless otherwise specified , this includes not only when directly above (or directly below) other structures, but also when above (or below) other structures, i.e. above (or below) other structures and in between another Including cases where components are included.

In this disclosure, (meth)acrylic refers to acrylic or methacrylic, respectively, and (meth)acrylate refers to acrylate or methacrylate, respectively.
In this specification, the terms "plate", "sheet", and "film" are not to be distinguished from each other based only on the difference in designation, and are referred to as "film surface (plate surface, sheet surface)". is the plane direction of the target film-like member (plate-like member, sheet-like member) when the target film-like member (plate-like member, sheet-like member) is viewed as a whole and in perspective point to
In the present disclosure, "energy ray" refers to electromagnetic waves (gamma rays, X rays, ultraviolet rays, visible rays, infrared rays, microwaves, etc.) that have the function of generating chemical species that initiate the required reaction, or particle rays (electron radiation, α-rays, neutron beams, various atomic beams, etc.). Examples of energy rays preferably used in the present invention include ultraviolet rays, visible rays and electron rays.
Hereinafter, the block copolymer, surface conditioner, adhesive composition, adhesive sheet, adhesive protective sheet, laminate, optical member and electronic member of the present disclosure will be described in detail in order.

A. Block copolymer A block copolymer of one embodiment of the present disclosure includes an A block containing a structural unit represented by the following general formula (I), and a B block containing a structural unit represented by the following general formula (II) It is a block copolymer having blocks.

（一般式（Ｉ）中、Ｒ^１は、水素原子又はメチル基、Ｒ^２は、置換基を有していても良く、炭素鎖中に酸素原子が含まれていても良い１価の炭化水素基を表し、
一般式（ＩＩ）中、Ｒ^３は、水素原子又はメチル基、Ｌ^１は、－ＣＯＯ－、－ＯＣＯ－、－Ｏ－、－ＣＯＮＨ－、－ＣＯＳ－、又は直接結合、Ｌ^２は、－Ｏ－、－ＮＨ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＯＮＨ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＮＨＣＯＮＨ－、及び－Ｓｉ（Ｒ^Ｌａ）（Ｒ^Ｌｂ）－からなる群から選択される１種以上が含まれていても良く、水酸基で置換されていても良い炭素数１～１５の炭化水素基を含む２価の基、又は直接結合、Ｒ^４～Ｒ^８は、それぞれ独立に、炭素数１～２０の置換基を有していても良い１価の炭化水素基、水素原子、水酸基、炭素数１～２０のアルコキシ基、又は下記一般式（ＩＩＩ）で表される基を表し、Ｒ^Ｌａ及びＲ^Ｌｂは、それぞれ独立に、炭素数１～２０の置換基を有していても良い１価の炭化水素基、水素原子、水酸基、又は炭素数１～２０のアルコキシ基を表し、ａは１～５０の整数である。）

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is a monovalent hydrocarbon which may have a substituent and which may contain an oxygen atom in the carbon chain. represents the group,
In general formula (II), R ³ is a hydrogen atom or a methyl group, L ¹ is -COO-, -OCO-, -O-, -CONH-, -COS-, or a direct bond, and L ² is - the group consisting of O-, -NH-, -S-, -COO-, -OCO-, -OCONH-, -NHCO-, -CONH-, -NHCONH-, and -Si(R ^La )(R ^Lb )- a divalent group containing a hydrocarbon group having ¹ to ¹⁵ carbon atoms which may be substituted with a hydroxyl group, or a direct bond; Each independently, a monovalent hydrocarbon group optionally having a substituent of 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or represented by the following general formula (III) R ^La and R ^Lb are each independently a monovalent hydrocarbon group optionally having a substituent of 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, or a represents an alkoxy group, and a is an integer of 1-50. )

（一般式（ＩＩＩ）中、Ｒ^９～Ｒ^１３は、それぞれ独立に、炭素数１～２０の置換基を有していても良い１価の炭化水素基、水素原子、水酸基、又は炭素数１～２０のアルコキシ基を表し、ｂは０～５０の整数である。）

(In general formula (III), R ⁹ to R ¹³ are each independently a monovalent hydrocarbon group optionally having a substituent of 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, or a represents an alkoxy group of ~20, and b is an integer of 0 to 50.)

{A block}
(Structural Unit Represented by Formula (I))
In general formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is a monovalent hydrocarbon group which may have a substituent and which may contain an oxygen atom in the carbon chain. represents
Examples of hydrocarbon groups for R ² include alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, aralkyl groups, and aryl groups.
The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2- Ethylhexyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like can be mentioned.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. Although the position of the double bond of the alkenyl group is not limited, it is preferable that the alkenyl group has a double bond at the terminal from the viewpoint of the reactivity of the resulting polymer.
Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12.
Aralkyl groups include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.

The hydrocarbon group may contain an oxygen atom in the carbon chain. Examples of the hydrocarbon group containing an oxygen atom in the carbon chain include -[CH(R ²¹ )-CH(R ²² )-O] _x -R ²³ or -[(CH ₂ ) _y -O] and _R ²¹ and R ²² are each independently a hydrogen atom or a methyl group, and R ²³ is a hydrogen atom, a hydrocarbon group, ^—CHO , —CH ₂ CHO or a monovalent group represented by —CH ₂ COOR ²⁴ , where R ²⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The hydrocarbon group for R ²³ can be the same as those shown for R ² above.
R ²⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and may be linear, branched or cyclic.
In the above, x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2.

Further, the hydrocarbon in which an oxygen atom may be contained in the carbon chain may have a substituent, and examples of the substituent include a halogen atom such as F, Cl, and Br, a nitro group, and a hydroxyl group. , an epoxy group, a carboxy group, an isocyanate group, an amino group, a carboxylic acid amide group, and the like.
The alkyl group may be used as the substituent of the aromatic ring such as the aryl group and the aralkyl group.
In addition, the number of carbon atoms of the substituent is not included in the preferable number of carbon atoms.

The structural unit of the A block may be appropriately selected so as to function as an affinity site for the mixed resin.
The structural unit represented by formula (I) may be contained singly or in combination of two or more in the A block of the copolymer. Two or more structural units contained in the A block may be arranged randomly within the block.

R ² is preferably selected so as to have excellent compatibility with the resin to be mixed. Specifically, for example, the resin to be mixed contains a structural unit derived from (meth)acrylic acid alkyl ester. When using a (meth)acrylic acid ester polymer containing, a methyl group, an ethyl group, an isobutyl group, an n-butyl group, an alkyl group having 1 to 18 carbon atoms such as a 2-ethylhexyl group, and further a carbon number of 1 to It preferably contains 12 alkyl groups.

Furthermore, the above R ² includes those having a crosslinkable group as a substituent, for example, by fixing the copolymer to the coating film surface by the crosslinkable group, the effect of imparting to the surface such as peelability It is preferable from the point that it becomes easy to continue.
Examples of crosslinkable groups include hydroxyl groups, epoxy groups, isocyanate groups, carboxy groups, amino groups and the like. The crosslinkable group contained in the A block is one or more selected from the group consisting of a hydroxyl group, an epoxy group, a carboxyl group, and an amino group, from the viewpoint of stability during polymerization and storage of the polymer. Among them, a hydroxyl group is preferable from the viewpoint of high stability and excellent reactivity of the thermal cross-linking agent.

The A block preferably contains a structural unit derived from a monomer containing a crosslinkable group from the viewpoint of making it easier to maintain the effect on the surface such as peelability by fixing the copolymer, and further , From the viewpoint of stability during polymerization and storage of the polymer, it preferably contains a monomer-derived structural unit containing one or more selected from the group consisting of a hydroxyl group, an epoxy group, a carboxy group, and an amino group. . Among them, it is preferable that the A block contains a structural unit derived from a hydroxyl group-containing monomer, from the viewpoint of high stability and excellent reactivity of the thermal cross-linking agent.
The A block may contain two or more types of structural units derived from a monomer containing a crosslinkable group.
The structural unit derived from a monomer containing a crosslinkable group may be a structural unit represented by the general formula (I), or may be a structural unit not applicable to the structural unit represented by the general formula (I). may be a structural unit having a structure of From the standpoint of polymerizability and ease of production, the structural unit derived from a monomer containing a crosslinkable group has a crosslinkable group as a substituent at R ² among the structural units represented by the general formula (I). It is preferably at least one selected from the group consisting of units and structural units derived from (meth)acrylic acid.

Examples of monomers that induce structural units derived from hydroxyl group-containing monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylates, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl acrylate, glycerin mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate and the like.

Examples of monomers that induce structural units derived from epoxy group-containing monomers include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate and the like.
Examples of monomers that induce structural units derived from isocyanate group-containing monomers include 2-(meth)acryloyloxyethyl isocyanate and alkylene oxide adducts thereof.
Examples of monomers that derive structural units derived from amino group-containing monomers include ethylaminoethyl (meth)acrylate and dimethylaminoethyl (meth)acrylate.
Monomers that derive structural units derived from carboxy group-containing monomers include, for example, (meth) acrylic acid, vinyl benzoic acid, maleic acid, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, and maleic anhydride. and phthalic anhydride, an addition reaction product with a cyclic anhydride such as cyclohexanedicarboxylic anhydride, and ω-carboxy-polycaprolactone mono(meth)acrylate. Among them, (meth)acrylic acid is preferable from the viewpoint of copolymerizability, cost, solubility, and the like.

The A block may have a structural unit other than the structural unit represented by general formula (I) within the scope of achieving the purpose of the present disclosure, and together with the structural unit represented by general formula (I) Any polymerizable structural unit can be contained. For example, structural units other than the structural units represented by general formula (I) include structural units derived from a monomer containing a crosslinkable group that does not correspond to the structural units represented by general formula (I), Structural units derived from other monomers having ethylenically unsaturated bonds are included.
In the A block in the block copolymer, the content ratio of the structural unit represented by the general formula (I) is, from the viewpoint of compatibility with other resins, etc., relative to the total mass of all the structural units of the A block. , preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less.
Further, as described above, a monomer-derived structural unit containing a crosslinkable group that does not correspond to the structural unit represented by the general formula (I) may be included, and the A block in the block copolymer , The total content ratio of the structural unit represented by the general formula (I) and the structural unit derived from a monomer containing a crosslinkable group that does not correspond to the structural unit represented by the general formula (I) is the adhesive From the viewpoint of compatibility with resins and the like in the composition, it is preferably 50% by mass or more and 100% by mass or less, and 70% by mass or more and 100% by mass or less, relative to the total mass of all structural units of the A block. It is more preferable to have
In addition, the content ratio of the structural units in the block copolymer can be obtained from the charged mass at the time of production. Moreover, the content ratio of the structural unit can be measured by a nuclear magnetic resonance spectrometer (NMR).

In the A block of the block copolymer, the content ratio of the structural unit represented by the general formula (I) having no crosslinkable group is 100% by mass with respect to the total mass of all structural units of the A block. However, it is preferably 90% by mass or less, more preferably 80% by mass or less, from the viewpoint of fixing it to the adhesive layer, suppressing contamination of the adherend, and maintaining the peelability effect. preferable. On the other hand, from the viewpoint of compatibility with other resins, the content ratio of the structural unit represented by the general formula (I) having no crosslinkable group is It is preferably 50% by mass or more, more preferably 70% by mass or more.

In the A block in the block copolymer, the content ratio of the monomer-derived structural unit containing a crosslinkable group may be 0% by mass with respect to the total mass of all structural units in the A block, but the adhesive layer It is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoints of fixing to the adherend, suppressing contamination of the adherend, and maintaining the releasability effect. On the other hand, from the viewpoint of compatibility with other resins, the content of structural units derived from a monomer containing a crosslinkable group should be 50% by mass or less with respect to the total mass of all structural units of the A block. is preferred, and it is more preferably 30% by mass or less.

Moreover, the total mass of all structural units of the A block including the structural unit represented by the general formula (I) is not particularly limited as long as it is appropriately adjusted according to the application such as the resin to be mixed. From the viewpoint of compatibility with other resins, the total mass of all structural units of the A block including the structural units represented by the general formula (I) is relative to the total mass of all structural units of the block copolymer. , is preferably 50% by mass or more, more preferably 70% by mass or more. On the other hand, from the viewpoint of imparting peelability, the total mass of all structural units of the A block including the structural unit represented by the general formula (I) is relative to the total mass of all structural units of the block copolymer. , is preferably 90% by mass or less, more preferably 80% by mass or less.

{B block}
The B block is a block that does not contain the structural unit represented by the general formula (I) but contains the structural unit represented by the general formula (II).
In general formula (II), L ¹ represents -COO-, -OCO-, -O-, -CONH-, -COS-, or a direct bond. Here, the direct bond means that L ¹ does not have an atom, that is, C (carbon atom) in general formula ( ^II ) and L ² , or Si (silicon atom ) means that they are bonded without intervening other atoms.
In general formula (II), L ¹ is preferably -COO- from the viewpoint of ease of synthesis.

In the general formula (II), L ² is -O-, -NH-, -S-, -COO-, -OCO-, -OCONH-, -NHCO-, -CONH-, -NHCONH- and - may contain one or more selected from the group consisting of Si(R ^La )(R ^Lb )—, and may contain a hydrocarbon group having 1 to 15 carbon atoms which may be substituted with a hydroxyl group. represents a group or a direct bond. R 1 ^La and R 2 ^Lb each independently represent an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms. . The optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms and the alkoxy group having 1 to 20 carbon atoms in R 1 ^La and R 2 ^Lb are the same as R ⁴ to R ⁸ described later. It's fine.

Specifically, L2 is a methylene group, an ethylene group, a propylene group ⁽ trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), a pentamethylene group, a hexamethylene group, an octamethylene group, Alkylene groups such as cyclohexylene groups, arylene groups such as phenylene groups, combinations of two or more of these groups (alkylene-arylene groups, etc.), cyclohexyleneoxy groups, —(CH ₂ ) ₂ —O—(CH ₂ ) ₂ -, -(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -, -CH(CH ₃ )CH ₂ -O-CH(CH ₃ )CH ₂ -, -(CH ₂ ) ₄ -O-(CH ₂ ) ₄ -, -(CH ₂ ) ₃ -O-, -(CH ₂ ) ₁₀ -Si(OCH ₃ )(OCH ₃ )-O-(CH ₂ ) ₂ -O- (CH ₂ ) ₃ —O—, —CH(CH ₂ OH)CH ₂ —O—, —CH(CH ₂ OH)CH ₂ —O—(CH ₂ ) ₃ —, —CH ₂ CH(OH)CH ₂ -NH-(CH ₂ ) ₃ -, -CH ₂ CH(OH)CH ₂ -S-(CH ₂ ) ₂ -, -CH ₂ CH(OH)CH ₂ -O-(CH ₂ ) ₂ -, -( CH ₂ ) ₂ -O-CH ₂ -CH(CH ₂ OH)-OCO-(CH ₂ ) ₂ -, -CH ₂ -CH(CH ₂ OH)-OCO-(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -OCONH-(CH ₂ ) ₆ -NHCONH-(CH ₂ ) ₃ - and the like.
In the general formula (II), L ² is preferably an alkylene group having 1 to 15 carbon atoms, especially an alkylene group having 2 to 10 carbon atoms, from the viewpoint of localization at the interface effectively. is more preferred, and an ethylene group, a propylene group, and a butylene group are even more preferred.

In the general formula (II), R ⁴ to R ⁸ are each independently a monovalent hydrocarbon group optionally having a substituent of 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, or a 20 alkoxy group or the group represented by the general formula (III). In general formula (III), each of R ⁹ to R ¹³ is independently an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, or a represents an alkoxy group of 1 to 20;
As the optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms in R ⁴ to R ⁸ and R ⁹ to R ¹³ , a hydrocarbon group having 1 to 10 carbon atoms is preferable, and specific is an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a benzyl group or a phenethyl group; hydroxypropyl group, cyanoethyl group, 1-chloropropyl group, 3,3,3-trifluoropropyl, in which some or all of the hydrogen atoms bonded to the carbon atoms of are substituted with a hydroxy group, a cyano group, a halogen atom, etc. and the like.
The alkoxy group having 1 to 20 carbon atoms in R ⁴ to R ⁸ and R ⁹ to R ¹³ is preferably an alkoxy group having 1 to 10 carbon atoms, specifically methoxy group, ethoxy group, propoxy group and butoxy group. etc. R ⁴ to R ⁸ are preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms. R ⁴ to R ⁸ and R ⁹ to R ¹³ are preferably alkyl groups or aryl groups, more preferably alkyl groups having 1 to 5 carbon atoms.

In general formula (II), a is an integer of 1 to 50, preferably an integer of 5 to 45, more preferably an integer of 10 to 40.
In general formula (III), b is an integer of 0 to 50, preferably an integer of 0 to 40, more preferably an integer of 0 to 30.

Specific examples of the structural unit represented by formula (II) include, but are not limited to, the following. In the formula below, OMe represents a methoxy group and Ph represents a phenyl group. In the formula, c, d, e, and f are 1≤c≤15, 1≤d≤30, 0≤e≤30, 1≤d+e≤50, 0≤f≤30, 1≤d+f≤50, 0≦g≦30 and 1≦h≦30.
A commercially available product may be used, for example, Silaplane FM-0711 manufactured by JNC.

The B block does not prevent the inclusion of structural units other than the structural unit represented by general formula (II) as long as the object of the present disclosure is achieved.
In the B block in the block copolymer, the content of the structural unit represented by the general formula (II) is 50% by mass with respect to the total mass of all the structural units of the B block from the viewpoint of exhibiting peelability. It is preferably 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and even more preferably 100% by mass. The content ratio of the structural unit is calculated from the charged mass when synthesizing the B block.

In addition, the total mass of all structural units of the B block including the structural unit represented by the general formula (II) is not particularly limited as long as it is appropriately adjusted according to the application of the mixed resin or the like. The total mass of all the structural units of the B block including the structural unit represented by the general formula (II) is 10% by mass from the viewpoint of imparting peelability to the total mass of all the structural units of the block copolymer. It is preferably 20% by mass or more, and more preferably 20% by mass or more. On the other hand, from the viewpoint of compatibility with other resins that have high transparency, are localized on the adhesive layer surface, and are compatible with other resins, the sum of all structural units of the B block including the structural units represented by the general formula (II) The mass is preferably 50% by mass or less, more preferably 30% by mass or less, relative to the total mass of all structural units of the block copolymer.

The mass-average molecular weight Mw of the block copolymer is preferably 2,000 to 200,000, more preferably 5,000 to 100,000, in order to improve the orientation of the adhesive layer to the surface. is more preferably 10,000 to 50,000.
Here, the mass average molecular weight (Mw) is determined by gel permeation chromatography (GPC) as a standard polystyrene conversion value.
In addition, in the present invention, the mass average molecular weight Mw of the block copolymer is determined by GPC (gel permeation chromatography) as a standard polystyrene conversion value. The measurement is performed using HLC-8220GPC manufactured by Tosoh Corporation, the elution solvent is N-methylpyrrolidone (NMP) to which 0.01 mol / liter of lithium bromide is added, and the polystyrene standard for the calibration curve is Mw: 8 ×. 10 ⁵ (F-80), Mw: 4×10 ⁵ (F-40), Mw: 2×10 ⁵ (F-20), Mw: 1×10 ⁵ (F-10), Mw: 4×10 ⁴ (F-4), Mw: 2×10 ⁴ (F-2), Mw: 5×10 ³ (A-5000), Mw: 2.5×10 ³ (A-2500), Mw: 1×10 ³ (A-1000), Mw: 5×10 ² (A-500) (manufactured by Tosoh Corporation), and TSK-GEL ALPHA-M×2 columns (manufactured by Tosoh Corporation). Block polymer intermediates (polymer intermediates containing only A block or B block) and macromonomers, which are raw materials for block copolymers, are also processed under the above conditions.

Further, the molecular weight distribution (Mw/Mn), which is the ratio of the mass average molecular weight Mw to the number average molecular weight Mn of the block copolymer, improves compatibility, leveling, and alignment,
It is preferably 1.00 to 1.99, more preferably 1.00 to 1.50, and even more preferably 1.00 to 1.30.
The number average molecular weight Mn of the block copolymer can also be measured using GPC in the same manner as the mass average molecular weight Mw.

In the present invention, the arrangement of each block of the block copolymer is not particularly limited, but AB block copolymers or BAB block copolymers are preferable from the viewpoint of improving orientation to the surface, and further AB block copolymers are preferred.

The method for producing the block copolymer is not particularly limited, and the block copolymer can be produced by a known method. Among them, the living polymerization method is preferred. This is because chain transfer and deactivation are unlikely to occur, and a copolymer having a uniform molecular weight can be produced. Among them, the block produced first is a reversible addition-fragmentation chain transfer (RAFT) type radical polymerization (hereinafter referred to as RAFT polymerization) or an atom transfer radical polymerization (Atom Transfer Radical Polymerization: ATRP). ) is preferably manufactured by When polymerized by RAFT polymerization or atom transfer radical polymerization, chain transfer and deactivation are unlikely to occur, and in particular, a polymer with uniform molecular weight can be produced, and compatibility, leveling, orientation, etc. can be improved. This is because coalescence can be obtained.
A copolymer can be produced by sequentially polymerizing monomers by these methods. For example, a block copolymer can be produced by first producing the A block and then polymerizing the structural units constituting the B block onto the A block. Also, the order of polymerization of the A block and the B block can be reversed in the above production method. Among them, the block copolymer is produced by first producing the A block by RAFT polymerization or atom transfer radical polymerization, and then polymerizing the structural units constituting the B block on the A block, from the viewpoint of facilitating living polymerization. preferable.
When at least the first block is polymerized by RAFT polymerization or atom transfer radical polymerization, the B block is directly attached to the main chain of the A block without the initiator residue or the like entering the connecting portion of the A block and the B block. It becomes a copolymer having a structure in which the main chain is bonded.

The block copolymers of the present disclosure have polysiloxane structures localized to the side chains of the B blocks. Therefore, when forming a film, the block copolymer of the present disclosure can be easily gathered on the surface while improving compatibility with the resin to be mixed. It can be suitably used as a surface conditioner with improved properties that can be imparted to the surface due to the polysiloxane structure, such as oiliness, antifouling properties, slip properties, and leveling properties. Since the block copolymer of the present disclosure can improve compatibility with the resin to be mixed, it is possible to suppress an increase in the haze value of the obtained film and obtain a film with good transparency. .
Among them, in the block copolymer of the present disclosure, when the A block contains a monomer-derived structural unit having a crosslinkable group, a crosslinkable group contained in the A block can be immobilized on the membrane surface by appropriately using a crosslinker. be done. Therefore, in this case, the durability of performance that can be imparted to the surface, such as releasability, is increased.

B. Surface conditioner
The surface control agent of the present disclosure is the block copolymer of the present disclosure.
Since the block copolymer of the present disclosure is as described above, the description is omitted here.
Since the surface conditioner of the present disclosure has a polysiloxane structure localized in the side chain of the B block of the block copolymer of the present disclosure, it is compatible with a resin mixed when forming a film. Although it is good, it is easy to gather on the surface, and even if it is added in a relatively small amount, it can effectively and uniformly impart performance to the surface. Therefore, the surface conditioner of the present disclosure suppresses the demerits that may occur by mixing a polysiloxane structure, while suppressing peelability, mold release, water/oil repellency, antifouling property, slipperiness, leveling property, etc. The polysiloxane structure can improve the properties that can be imparted to the surface.
In addition, as described above, when the A block of the block copolymer of the present disclosure contains a structural unit derived from a monomer having a crosslinkable group, the surface conditioner of the present disclosure can be used to form a film by using the crosslinkable group. It becomes possible to immobilize it on the surface, and the durability of the performance that can be imparted to the surface by the surface conditioner increases.

C. Adhesive composition The adhesive composition of one embodiment of the present disclosure contains an energy ray-curable component containing a (meth)acrylic acid ester-based polymer, an energy ray initiator, and the block copolymer of the present disclosure. do.
The adhesive composition of one embodiment of the present disclosure contains an energy ray-curable component containing a (meth) acrylic acid ester polymer, an energy ray initiator, and the block copolymer of the present disclosure. It is possible to reduce the peeling force from the member to be protected when peeling, and to form an adhesive layer excellent in easy peelability from the member to be protected.

The adhesive layer formed using the adhesive composition of one embodiment of the present disclosure contains an energy ray-curable component containing a (meth)acrylic acid ester-based polymer and an energy ray initiator. By curing the energy ray-curable component by irradiation, it has a characteristic that the adhesive strength decreases from the initial adhesive strength, and furthermore, since the block copolymer of the present disclosure is localized on the surface, The adhesive strength after energy beam irradiation is greatly reduced. Therefore, the adhesive layer formed using the adhesive composition of one embodiment of the present disclosure has good adhesive strength when used when adhesive strength is required, and has adhesive properties such that the adhesive layer can be peeled off from the member to be protected. When the force is no longer required, it is possible to form an adhesive layer with excellent easy peelability from the member to be protected.

{Energy ray-curable component containing (meth)acrylic acid ester polymer}
The energy ray-curable component containing the (meth)acrylate polymer used in the adhesive composition of one embodiment of the present disclosure includes (i) the (meth)acrylate polymer and the energy ray-curable polymer. When the composition contains a functional compound, (ii) the (meth)acrylic acid ester-based polymer has two or more energy ray-curable functional groups in one molecule, and the energy ray-curable polyfunctional compound is not included. Among them, the energy ray-curable component containing a (meth)acrylic acid ester-based polymer contains (i) a (meth)acrylic acid ester-based polymer and an energy ray-curable polyfunctional compound to improve adhesive strength. is preferable because it is easy to adjust the In the case of (i) above, the (meth)acrylate polymer may have an energy ray-curable functional group.

((Meth)acrylic acid ester polymer)
As the (meth)acrylic acid ester polymer, it is preferable to use a (meth)acrylic acid ester copolymer obtained by copolymerizing a (meth)acrylic acid ester used as an acrylic pressure-sensitive adhesive with another monomer. .
(Meth)acrylic acid ester-based polymers include, among others, a structural unit derived from a (meth)acrylic acid alkyl ester monomer having a linear or branched alkyl group having 1 to 20 carbon atoms, and a monomer derived from a crosslinkable group-containing monomer. It is preferable to use a (meth)acrylic acid ester-based copolymer having a structural unit. The (meth)acrylic acid ester copolymer can be crosslinked by using the crosslinkable groups introduced into the molecule of the (meth)acrylic acid ester polymer, and improves the cohesive force of the adhesive composition. , it is possible to obtain an adhesive layer having a good balance between easy peelability and durability under a predetermined environment.

Examples of (meth)acrylic acid alkyl ester monomers having a linear or branched alkyl group having a carbon number of 1 or more and 20 or less include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n - butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl ( meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n- Hexadecyl (meth)acrylate, n-octadecyl (meth)acrylate and the like may be used alone or in combination of two or more. Among them, (meth)acrylic acid alkyl esters having a linear or branched alkyl group having 4 to 14 carbon atoms are preferred from the viewpoint of exhibiting wettability and adhesiveness to the adherend, and linear alkyl esters having 7 to 13 carbon atoms. or a (meth)acrylic acid alkyl ester having a branched alkyl group is more preferable.

As the crosslinkable group-containing monomer used in the (meth)acrylic acid ester-based polymer, the same crosslinkable group-containing monomer as used in the above-described block copolymer of the present disclosure can be used.
That is, examples of crosslinkable groups include hydroxyl groups, epoxy groups, isocyanate groups, carboxy groups, and amino groups.
From the viewpoint of stability during polymerization and storage of the polymer, it preferably contains a monomer-derived structural unit containing one or more selected from the group consisting of a hydroxyl group, an epoxy group, a carboxy group, and an amino group, Containing a structural unit derived from a hydroxyl group-containing monomer is preferable from the viewpoint of high stability and excellent reactivity of the thermal cross-linking agent.

Further, the (meth)acrylic acid ester-based polymer may further have an energy ray-curable functional group in its side chain.
The energy ray-curable functional group preferably has an ethylenically unsaturated bond, and is preferably a (meth)acryloyl group, a vinyl group, an allyl group, or the like.
As a method for introducing an energy ray-curable functional group into the side chain of the (meth)acrylic acid ester-based polymer, a conventionally known production method may be appropriately selected and used.
For example, a (meth)acrylic acid ester polymer having a carboxy group is reacted with glycidyl (meth)acrylate, or a (meth)acrylic acid ester polymer having an isocyanate group is reacted with hydroxyethyl (meth)acrylate. 2-isocyanatoethyl (meth)acrylate can be reacted with a (meth)acrylic acid ester polymer having a hydroxyl group to add an energy ray-curable functional group.

In addition, the (meth)acrylic ester-based polymer may contain structural units derived from other monomers within the range of functioning as an acrylic pressure-sensitive adhesive.
Other monomers that can be used include, for example, rigid monomers such as cyclohexyl methacrylate, benzyl methacrylate, and adamantyl methacrylate.

Since the (meth)acrylic acid ester monomer is the main component constituting the (meth)acrylic acid ester polymer, the lower limit of the content is usually set to 50% by mass with respect to the total monomer components (100% by mass). Among them, the lower limit of the content of the (meth)acrylic acid alkyl ester monomer is preferably 50% by mass or more, more preferably 60% by mass or more, and 80% by mass or more. It is more preferable that the content is 90% by mass or more.
Furthermore, the upper limit of the content of the (meth)acrylic acid alkyl ester monomer is preferably 99.5% by mass or less, more preferably 99% by mass or less, relative to the total monomer components (100% by mass). More preferably, it is 98% by mass or less.

The crosslinkable group-containing monomer may be appropriately selected from the viewpoint of the balance between adhesive strength and peeling strength, but the lower limit of the content is preferably 0.5% by mass or more, and 1% by mass or more. is more preferable, and 2% by mass or more is even more preferable.
Furthermore, the upper limit of the content of the crosslinkable group-containing monomer is preferably 15% by mass or less, more preferably 13% by mass or less, with respect to the total monomer component (100% by mass), and 10% by mass. % or less is more preferable.

Other monomers in the (meth)acrylic acid ester-based polymer may be appropriately selected from the viewpoint of the balance between adhesive strength and peeling strength and the performance to be imparted, and may be 0% by mass or more and 49.5% by mass or less. , is preferably 39% by mass or less, more preferably 18% by mass or less.

When the (meth)acrylic acid ester polymer has an energy ray-curable functional group in the side chain, the content of the monomer used in the structural unit having the energy ray-curable functional group is effective for light peeling. Therefore, it is preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass or more based on the total (100% by mass) of the (meth)acrylic acid ester polymer. is even more preferable. On the other hand, the content of the energy ray-curable functional group is preferably 50% by mass or less, more preferably 40% or less, from the viewpoint of exhibiting adhesiveness.
The content of the monomers used in the structural unit having an energy ray-curable functional group is calculated by the total content of the monomers used in the structural unit. ) When a structural unit having an energy ray-curable functional group is prepared by reacting acrylate (GMA), the content of monomers used in the structural unit having an energy ray-curable functional group is the sum of MAA and GMA Calculated in quantity.

The mass average molecular weight of the (meth)acrylic acid ester polymer is preferably 100,000 to 5,000,000, more preferably 200,000 to 4,000,000, and still more preferably, from the viewpoint of improving adhesive strength and peeling strength. is 300,000 to 3,000,000, more preferably 400,000 to 1,000,000. If the mass-average molecular weight is less than 100,000, the cohesive force may be reduced, leaving adhesive residue on the surface of the adherend after peeling, resulting in uniform wettability and adhesion on the surface of the adherend after peeling. There is a risk that the effect of sex may not be obtained. On the other hand, if the weight average molecular weight exceeds 5,000,000, the wettability of the surface of the adherend after peeling off the adhesive layer may be insufficient.

The glass transition temperature (Tg) of the (meth)acrylic acid ester polymer is preferably 0° C. or lower, more preferably -10° C. or lower, from the viewpoint of improving adhesive strength and peeling strength. If the glass transition temperature is higher than 0°C, the wettability of the adherend surface after peeling the adhesive layer may be insufficient. The glass transition temperature of the (meth)acrylic acid ester polymer can be adjusted by changing the composition ratio of the monomer components constituting the (meth)acrylic acid ester polymer.

Moreover, the hydroxyl value of the (meth)acrylic acid ester-based polymer is preferably 0.1% by mass or more and 10% by mass or less from the viewpoint of the balance between the shape retention property and adhesive strength of the adhesive protective sheet. The hydroxyl value here represents the amount of hydroxyl groups (the amount of OH groups) in 1 g of the acrylic acid ester-based copolymer, and can be obtained from the mass ratio of the hydroxyl group-containing monomer and the acrylic acid ester by NMR measurement.

As the (meth)acrylic ester-based polymer, a commercially available acrylic adhesive may be used. (manufactured by Soken Chemical), SK Dyne 2950 (manufactured by Soken Chemical), SK Dyne 2094 (manufactured by Soken Chemical), Olivine EG-654 (manufactured by Toyochem) and the like can be preferably used.

(Energy ray-curable polyfunctional compound)
It is preferable to contain an energy ray-curable polyfunctional compound as the energy ray-curable component. Energy ray-curable polyfunctional compounds are monomers, oligomers, and polymers containing two or more energy ray-curable groups in one molecule. The polymer is a polymer different from the (meth)acrylic acid ester polymer used as the acrylic pressure-sensitive adhesive.
By containing an energy ray-curable polyfunctional compound, three-dimensional cross-linking is possible, and further, when the (meth)acrylic acid ester polymer has energy ray-curable properties, (meth)acrylic acid By reacting with the ester-based polymer, the (meth)acrylic acid ester-based polymer can be increased in molecular weight or three-dimensionally crosslinked.
By containing the energy ray-curable component, it is possible to easily control the adhesiveness to the substrate, cohesiveness, and the like in the case of forming the adhesive layer within a desired range.

Energy ray-curable polyfunctional compounds include, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate. ) acrylate, neopentyl glycol adipate di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphorus Acid di(meth)acrylate, di(meth)acryloxyethyl isocyanurate, allylated cyclohexyl di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, dimethyloldicyclopentane di(meth)acrylate, ethylene oxide Modified hexahydrophthalic acid di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, adamantane di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, etc. Bifunctional polyfunctional (meth) acrylate monomer, isocyanuric acid ethylene oxide modified triacrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate , pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, trifunctional polyfunctional (meth)acrylate monomers such as tris(meth)acryloxyethyl isocyanurate, diglycerin tetra(meth) Acrylate, tetrafunctional type such as pentaerythritol tetra(meth)acrylate, pentafunctional type polyfunctional (meth)acrylate monomer such as propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate , caprolactone-modified dipentaerythritol hexa(meth)acrylate and other hexafunctional polyfunctional (meth)acrylate monomers, and intramolecular compounds called urethane (meth)acrylates, polyester (meth)acrylates, and epoxy (meth)acrylates. have several (meth)acryloyl groups in the molecular weight of several hundred to several thousand can be preferably used. Energy ray-curable polyfunctional compounds can be used singly or in combination of two or more.

Among the energy ray-curable polyfunctional compounds, from the viewpoint of the balance between adhesive strength and peel strength, there are several compounds in the molecule called urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate. It is preferable to use an oligomer having a (meth)acryloyl group and having a molecular weight of several hundred to several thousand.

The content of the energy ray-curable polyfunctional compound is preferably 10 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic acid ester polymer.
This is because if the content of the energy ray-curable polyfunctional compound is less than 10 parts by mass, the effect of addition may not be exhibited. On the other hand, if the content of the energy ray-curable polyfunctional compound exceeds 300 parts by mass, the properties of the adhesive composition such as storage stability, substrate adhesion, adhesiveness, or releasability may be remarkably lowered. is.
Therefore, the lower limit of the content of the energy ray-curable polyfunctional compound is more preferably 20 parts by mass or more, more preferably 50 parts by mass or more, relative to 100 parts by mass of the (meth)acrylic acid ester polymer. is more preferred.
In addition, the upper limit of the content of the energy ray-curable polyfunctional compound is more preferably 250 parts by mass or less, more preferably 200 parts by mass or less, relative to 100 parts by mass of the (meth)acrylic acid ester polymer. is more preferable, and 150 parts by mass or less is particularly preferable.

The total content of the energy ray-curable component containing the (meth)acrylic acid ester polymer is 75% by mass or more based on the solid content of the adhesive composition, from the viewpoint of the balance of the peeling force after energy ray irradiation. and more preferably 80% by mass or more. In addition, the total content of the energy ray-curable component containing the (meth)acrylic acid ester-based polymer is, from the viewpoint of adhesive strength and suppression of contamination to the adherend, relative to the solid content of the adhesive composition, It is preferably 99% by mass or less, more preferably 95% by mass or less.
In addition, in this specification, solid content means all the components other than a solvent.

{energy beam initiator}
Any compound capable of generating radicals when irradiated with a predetermined amount of energy rays such as ultraviolet rays can be used as the energy ray initiator. Examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-( hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary-butylanthraquinone, 2-aminoanthraquinone, 2- Methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, oligo[2-hydroxy-2 -methyl-1[4-(1-methylvinyl)phenyl]propanone], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like alone or in combination of two or more.

The content of the energy ray initiator is preferably 0.5% by mass or more, and 1.0% by mass or more, based on the solid content of the adhesive composition, from the viewpoint of sufficiently curing the adhesive composition. is more preferable. In addition, the content of the energy ray initiator is preferably 10% by mass or less, and 5.0% by mass or less, relative to the solid content of the adhesive composition, from the viewpoint of the balance between adhesive strength and peeling strength. is more preferable.

{Block copolymer of the present disclosure}
The adhesive composition of the present disclosure contains the block copolymer of the present disclosure.
When an adhesive layer is formed using the adhesive composition of the present disclosure, the block copolymer of the present disclosure is localized on the surface of the adhesive layer, so that the adhesive strength of the adhesive layer after energy ray irradiation is greatly reduced. . By forming an adhesive layer using the adhesive composition of the present disclosure, it is possible to form an adhesive layer with excellent easy peelability.

When the block copolymer of the present disclosure used in the adhesive composition of the present disclosure has a structural unit derived from a crosslinkable group-containing monomer, it is fixed to the adhesive layer surface by reacting with a thermal cross-linking agent described later. It is preferable from the viewpoint that the adhesive layer can be easily peeled off from the adherend, and that migration of the block copolymer to the adherend can be suppressed when the pressure-sensitive adhesive layer is peeled off from the adherend.
Furthermore, when the block copolymer of the present disclosure used in the adhesive composition of the present disclosure has a structural unit derived from a crosslinkable group-containing monomer, the (meth)acrylic acid ester similarly having a crosslinkable group It is preferable from the viewpoint that the compatibility with the system polymer increases, the haze of the adhesive layer can be further reduced, and the transparency increases. If the haze can be suppressed and the transparency is high, for example, it is possible to perform precise confirmation of appearance defects with a camera or the like through the adhesive layer, and the adhesive layer can be suitably used as a removable adhesive sheet for processes. can.

The content of the block copolymer of the present disclosure is preferably 0.1% by mass or more with respect to the solid content of the adhesive composition from the viewpoint of effectively reducing the peeling force at the time of peeling. 0.5% by mass or more is more preferable. In addition, the content of the block copolymer of the present disclosure is preferably 5.0% by mass or less relative to the solid content of the adhesive composition from the viewpoint of transparency of the adhesive composition, and 3.0 % or less is more preferable.

{Thermal cross-linking agent}
The adhesive composition of the present disclosure preferably further contains a thermal cross-linking agent. A thermal cross-linking agent is a compound that promotes a cross-linking reaction by the action of heat.
By containing a thermal cross-linking agent in the adhesive composition of the present disclosure, it reacts with the crosslinkable group contained in the (meth) acrylic acid ester polymer to eliminate the fluidity of the adhesive composition itself after film formation. , the adhesive force or peeling force before energy beam irradiation can be adjusted.
Further, when the block copolymer of the present disclosure contained in the adhesive composition of the present disclosure has a crosslinkable group, the inclusion of a thermal cross-linking agent also reacts with the crosslinkable group of the block copolymer of the present disclosure. can be used to immobilize the block copolymer of the present disclosure on the surface of the adhesive layer. The pressure-sensitive adhesive layer formed in this way is preferable because it has excellent peelability and can suppress migration of the block copolymer to the adherend when the pressure-sensitive adhesive layer is peeled off from the adherend.

Examples of thermal cross-linking agents include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, aziridine-based cross-linking agents, and metal chelate-based cross-linking agents. Among these, the isocyanate-based cross-linking agent and the epoxy-based cross-linking agent are preferable in that the effects of the present disclosure are likely to be exhibited satisfactorily. The number of thermal cross-linking agents may be one, or two or more.

Examples of isocyanate-based cross-linking agents include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; Isocyanate, aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate, trimethylolpropane/tolylene diisocyanate trimer adduct (trade name "Coronate L" manufactured by Nippon Polyurethane Industry), trimethylolpropane/h Isocyanate adducts such as xamethylene diisocyanate trimer adduct (trade name “Coronate HL” manufactured by Nippon Polyurethane Industry) and isocyanurate form of hexamethylene diisocyanate (trade name “Coronate HX” manufactured by Nippon Polyurethane Industry) can be mentioned.

Epoxy cross-linking agents include, for example, bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylol. Propane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine (trade name "TETRAD-X" manufactured by Mitsubishi Gas Chemical), 1,3-bis ( N,N-diglycidylaminomethyl)cyclohexane (trade name “TETRAD-C” manufactured by Mitsubishi Gas Chemical) and the like.

The content of the thermal cross-linking agent may be appropriately adjusted depending on the balance between the adhesive force and the peeling force, but from the viewpoint of obtaining the above effect, it should be 1.0% by mass or more with respect to the solid content of the adhesive composition. is preferred, and 2.0% by mass or more is more preferred. Also, the content of the thermal cross-linking agent is
From the viewpoint of adhesiveness before energy irradiation, the content is preferably 10% by mass or less, more preferably 8.0% by mass or less, relative to the solid content of the adhesive composition.

{solvent}
It is preferable that the pressure-sensitive adhesive composition of the present disclosure further contains a solvent from the viewpoint of improving the coatability on the base material and the mixability of the ingredients.
The solvent can be appropriately selected and used from solvents that do not react with each component in the composition and are capable of dissolving or dispersing these components. Examples of solvents include esters, aromatic hydrocarbons, ketones, and ethers.
More specifically, methyl acetate, ethyl acetate, n-butyl acetate, i-butyl acetate, benzene, One or a combination of two or more of toluene, xylene, acetone, cyclohexane, cyclohexanone, methyl ethyl ketone, tetrahydrofuran and the like can be mentioned.

In addition, the content of the solvent may be adjusted as appropriate from the viewpoint of the applicability to the base material and the mixing properties of the ingredients. A content of 5% by mass or more and 40% by mass or less is preferable from the standpoint of coatability on substrates and the like and mixability of compounding components.

{Optional Additives}
The pressure-sensitive adhesive composition of the present disclosure may further contain various additives as necessary, as long as the object of the present disclosure is not impaired.
Examples of various additives include cross-linking accelerators, antioxidants, stabilizers, viscosity modifiers, tackifying resins, organic or inorganic fillers, and the like. Examples of cross-linking accelerators include triethylamine-based, cobalt naphthenate-based, tin-based, zinc-based, titanium-based, and zirconium-based accelerators. When the cross-linking agent is an isocyanate-based cross-linking agent, zinc-based, titanium-based and zirconium-based accelerators such as alkoxides, acylates and complexes, stannous chloride, tetra-n-butyltin, stannic chloride and trimethyltin hydroxide , dimethyltin dichloride, and di-n-butyltin dilaurate are preferably used.
Moreover, a phenol-type antioxidant etc. are mentioned as antioxidant. By including an appropriate amount of antioxidant in the pressure-sensitive adhesive composition of this example, it is possible to further suppress an increase in peel strength after heating when the pressure-sensitive adhesive layer is formed.

{Manufacture of adhesive composition}
The method for producing the adhesive composition is not particularly limited.
The adhesive composition can be obtained by adding each component described above and various additives added as necessary in an arbitrary order and dissolving or dispersing them. Mixing of the above components can be carried out using, for example, a mixer or kneader such as a dissolver, planetary mixer, or butterfly mixer.

D. Adhesive Sheet, Adhesive Protective Sheet The adhesive sheet of one embodiment of the present disclosure has an adhesive layer and a substrate disposed on one side of the adhesive layer,
The pressure-sensitive adhesive layer has a characteristic that the pressure-sensitive adhesive strength decreases from the initial pressure-sensitive adhesive strength due to energy ray irradiation, and the pressure-sensitive adhesive layer is a pressure-sensitive adhesive sheet that is a cured product of the pressure-sensitive adhesive composition of the present disclosure.

The pressure-sensitive adhesive sheet of one embodiment of the present disclosure is provided with a pressure-sensitive adhesive layer that is a cured product of the pressure-sensitive adhesive composition of the present disclosure, so that the same action as described in the pressure-sensitive adhesive composition provides sufficient adhesive strength during use. However, by reducing the adhesive strength from the initial adhesive strength by irradiating the energy beam before peeling, the peeling force from the adherend when peeling can be reduced, and the easy peeling from the adherend is excellent. It is an adhesive sheet.

Since the adhesive sheet is excellent in easy peelability from the adherend, it can be suitably used as a removable adhesive protective sheet that temporarily protects the adherend.

FIG. 1 shows a schematic cross-sectional view of an example of the pressure-sensitive adhesive sheet of the present disclosure.
As shown in FIG. 1 , the adhesive sheet 10 of the present disclosure includes an adhesive layer 1 and a substrate 2 arranged on one side of the adhesive layer 1 .

{adhesive layer}
The adhesive layer is a cured product of the adhesive composition of the present disclosure. Since the pressure-sensitive adhesive composition of the present disclosure has been described above, the description thereof is omitted here.
The film thickness of the adhesive layer can be appropriately adjusted depending on the purpose. For example, the thickness of the adhesive layer is preferably 100 µm or less, more preferably 90 µm or less, and even more preferably 80 µm or less. The lower limit of the film thickness is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 40 μm or more.

The adhesive layer has a peeling speed of 2.4 m / min and a peeling angle of 180 degrees against an acrylic plate adherend (trade name: Acrylite L001, manufactured by Mitsubishi Chemical) as an initial adhesive strength before irradiation with energy rays. , preferably 0.1 N/25 mm or more and 20 N/25 mm or less, more preferably 0.2 N/25 mm or more and 10 N/25 mm or less.
In addition, the adhesive layer was peeled at a peeling speed of 2.4 m / min and a peeling angle of 180 degrees against an acrylic plate adherend (trade name: Acrylite L001, manufactured by Mitsubishi Chemical) as an adhesive strength after energy ray irradiation. The force is preferably 0.05 N/25 mm or less, more preferably 0.03 N/25 mm or less, and even more preferably 0.02 N/25 mm or less. In general, the higher the peeling speed, the greater the peeling force.

The adhesive layer preferably has a total light transmittance of 80% or more, more preferably 90% or more, before being irradiated with energy rays. Further, the adhesive layer preferably has a haze of 1.5% or less, more preferably 1.0% or less, before being irradiated with energy rays. Here, the total light transmittance of the present disclosure can be measured according to JIS K7361-1, for example, by a haze meter (eg, HM150 manufactured by Murakami Color Research Laboratory). The haze value can be measured by a method conforming to JIS K-7105, for example, by a haze meter (eg HM150 manufactured by Murakami Color Research Laboratory).

{Base material}
The base material used for the pressure-sensitive adhesive sheet of the present disclosure may be appropriately selected and used, and is not particularly limited. It is preferable to use a transparent substrate since it is preferable to reduce the .
The substrate used for the adhesive sheet of the present disclosure preferably has a total light transmittance of 80% or more, more preferably 90% or more. Further, the haze of the base material used for the pressure-sensitive adhesive sheet of the present disclosure is preferably 1.5% or less, more preferably 1.0% or less.

The base material used for the pressure-sensitive adhesive sheet of the present disclosure preferably has heat resistance. , polyether imide resin, polyether ketone resin, polyphenylene sulfide resin, polyacrylate resin, polyester ether resin, polyamide imide resin, polymethyl methacrylate resin, fluorine resin, etc., and especially from the viewpoint of economy and performance. Preferred substrates include polyethylene terephthalate.

The film thickness of the base material may be appropriately selected according to the application of the pressure-sensitive adhesive sheet. The thickness of the material used as the material film, for example, a film thickness of about 10 to 125 μm is preferably used.

{Method for manufacturing adhesive sheet}
The pressure-sensitive adhesive sheet of the present disclosure can be produced by any suitable method.
The adhesive sheet of the present disclosure can be obtained by producing a laminate of a substrate and an adhesive layer. Such laminates are, for example,
(1) A method of applying an adhesive composition solution or a hot melt onto a substrate to form an adhesive layer,
(2) A method of transferring the adhesive layer coated and formed on the separator onto the base material according to (1) above,
(3) a method of extruding and applying the pressure-sensitive adhesive composition onto a substrate;
(4) A method of extruding a substrate layer and an adhesive layer in two layers or multiple layers,
can be manufactured by any suitable method, such as
Among them, the manufacturing method (1) is preferably used.

Moreover, the surface of the base material used for the pressure-sensitive adhesive sheet of the present disclosure can be optionally subjected to surface treatment. Examples of surface treatment at this time include (1) discharge treatment such as corona discharge treatment and glow discharge treatment, (2) plasma treatment, (3) flame treatment, (4) ozone treatment, (5) ultraviolet treatment and electron beam treatment. , ionizing active ray treatment such as radiation treatment, (6) surface roughening treatment such as sand mat treatment and hairline treatment, (7) chemical treatment, and (8) anchor layer formation. Polyurethane-based resins, polyester-based resins, acrylic-based resins, polyester-polyurethane resins, and the like are used as the anchor layer. The thickness of this anchor layer is usually in the range of 0.01 to 1.5 μm.

As a method for applying the pressure-sensitive adhesive composition to the base material, a known method can be appropriately selected and used. For example, gravure coating method, reverse coating method, knife coating method, dip coating method, spray coating method, air knife coating method, spin coating method, roll coating method, printing method, immersion pick-up method, curtain coating method, die coating method, casting method, bar coating method, extrusion coating method, E-type coating method, various printing methods, transfer method using a mold, and the like.

The adhesive composition layer applied on the base material can be made into an adhesive layer by appropriately removing (drying) the solvent and heating to thermally crosslink the thermal crosslinking agent.

The pressure-sensitive adhesive sheet of the present disclosure preferably has a total light transmittance of 80% or more, more preferably 90% or more, of the entire sheet (excluding the separator described later) before irradiation with energy rays.
In addition, the pressure-sensitive adhesive sheet of the present disclosure preferably has a haze of 1.5% or less, and more preferably 1.0% or less, of the entire sheet (excluding the separator described later) in a state before energy beam irradiation. preferable.
Such a range is preferable because the pressure-sensitive adhesive sheet has good transparency and the adherend can be precisely confirmed and inspected with a camera or the like while the pressure-sensitive adhesive sheet is attached.

In order to facilitate the handling of the pressure-sensitive adhesive sheet of the present disclosure, it is preferable to adhere a peelable separator to the surface of the pressure-sensitive adhesive layer until the pressure-sensitive adhesive sheet is adhered to an adherend. Any known separator can be used, such as a release PET film, and the thickness thereof can be, for example, about 15 to 200 μm.

The pressure-sensitive adhesive sheet of the present disclosure is a pressure-sensitive adhesive sheet that has sufficient adhesive strength when used, can reduce the peeling force from the adherend when peeled, and is excellent in easy peelability from the adherend. Since high transparency can also be obtained, it can be used as a suitable adhesive protective sheet for the following uses, which have been a problem in the past.
For example, when the surface of the member to be protected on which the protective sheet is attached has a large width and the force required to peel off the protective sheet from the member to be protected increases, or when various electronic members and optical members are made more precise. It can be used as a suitable adhesive protective sheet even when the protected member itself or the surface of the protected member is easily destroyed due to the thinning of the protected member itself, the integration of functions, and the miniaturization due to complication. It can also be suitably used as a re-peelable pressure-sensitive adhesive protective sheet for processes.

E. Laminate, optical member, electronic member A laminate of one embodiment of the present disclosure is a laminate of the adhesive protective sheet of the present disclosure and a member to be protected attached to the adhesive layer side of the adhesive protective sheet. be.
The adhesive protective sheet of the present disclosure is an adhesive protective sheet that has sufficient adhesive strength when used, can reduce the peeling force from the adherend when peeled, and is excellent in easy peelability from the adherend. In addition, since it can be made highly transparent, it can be easily re-peeled even as a protected member with a wide and wide area, or as a laminated body with the protected member itself or the protected member whose surface is easily destroyed. possible and does not adversely affect the member to be protected.

FIG. 2 shows a schematic cross-sectional view of an example of the laminate of the present disclosure.
As shown in FIG. 2, the laminate 100 of the present disclosure includes an adhesive protective sheet 20 having an adhesive layer 1 and a substrate 2 disposed on one side of the adhesive layer 1, and the adhesive protective sheet 20 and the member to be protected 11 adhered to the adhesive layer 1 side of is laminated.

For example, with conventional adhesive protective sheets, easy peelability is still insufficient, and there are problems to be solved. Examples of protected members include various optical members and various electronic members.
Optical members and electronic members can be suitably used as members to be protected in the laminate of the present disclosure.
That is, the optical member of one embodiment of the present disclosure is an optical member to which the adhesive protective sheet of the present disclosure is adhered.
Further, an electronic member of one embodiment of the present disclosure is an electronic member to which the adhesive protective sheet of the present disclosure is adhered.
The optical members and electronic members used in the present disclosure are not particularly limited, and conventionally known optical members and electronic members that require an adhesive protective sheet and their intermediate products can be appropriately selected and used. .

Hereinafter, the present disclosure will be specifically described with reference to Examples. These descriptions are not intended to limit the embodiments of the present disclosure.
The mass average molecular weight (Mw) and number average molecular weight (Mn) were measured by GPC (gel permeation chromatography). GPC measurement was performed using Tosoh's HLC-8220GPC, the elution solvent was NMP to which 0.01 mol/liter of lithium bromide was added, and the polystyrene standard for calibration curve was Mw: 8 × 10 ⁵ (F-80). Mw: 4×10 ⁵ (F-40), Mw: 2×10 ⁵ (F-20), Mw: 1×10 ⁵ (F-10), Mw: 4×10 ⁴ (F-4), Mw: 2×10 ⁴ (F-2), Mw: 5×10 ³ (A-5000), Mw: 2.5×10 ³ (A-2500), Mw: 1×10 ³ (A-1000), Mw: 5×10 ² (A-500) (manufactured by Tosoh), and TSK-GEL ALPHA-M×2 columns (manufactured by Tosoh) were used for measurement.

(Production Example 1: Production of block copolymer A)
(1) Synthesis of Block Polymer Intermediate 1 A reactor equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, digital thermometer, 4 g of ethyl acetate, n-butyl methacrylate (n-butyl methacrylate) purified by activated alumina (n- BMA) 4.2 g, 2-hydroxyethyl methacrylate (HEMA) 1.05 g, (mass ratio n-BMA/HEMA = 80/20), methyl-4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate 0.0657 g of (RAFT agent) (8% by mass added to 100% by mass of monomer), 0.00164 g of azobisisobutyronitrile (AIBN) (10% mol amount with respect to RAFT agent) was added, and nitrogen After bubbling for 10 minutes, the mixture was placed in a nitrogen atmosphere and stirred at 75° C. for 4 hours.
After 4 hours, the mixture was returned to room temperature, diluted with acetone, and reprecipitated with cold hexane to obtain 4.5 g of block polymer intermediate 1 as a solid. As a result of GPC measurement, the resulting block polymer intermediate 1 had a mass average molecular weight (Mw) of 10,000, a number average molecular weight (Mn) of 8,500, and a molecular weight distribution (PDI) (Mw/Mn) of 1.2.

(2) Synthesis of block copolymer A 2.4 g of block polymer intermediate 1 obtained above was placed in a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. Silaplane FM-0711 (manufactured by JNC, catalog values: In general formula (II), R ³ is a methyl group, L ¹ is -COO-, L ² is -(CH ₂ ) ₃ -, R ⁴ to R ⁷ are methyl 0.6 g of group, weight average molecular weight (weight average molecular weight of siloxane unit) 1000), 3 g of ethyl acetate, and 0.00657 g of AIBN (0.2% by mass with respect to 100% by mass of block polymer intermediate 1) were added. After nitrogen bubbling was performed for 10 minutes, the mixture was placed in a nitrogen atmosphere and stirred at 75° C. for 4 hours.
After 4 hours, the temperature was returned to room temperature, and a 50% mass solution of block copolymer A was obtained. As a result of GPC measurement, the block copolymer A thus obtained had an Mw of 11,000, an Mn of 9,000, and a PDI of 1.2.

(Production Examples 2 to 4: Production of block copolymers B to D)
In Production Examples 2 and 3, in Production Example 1, the RAFT agent and azobisisobutyronitrile (AIBN) used in producing the block polymer intermediate were changed to the mass ratios shown in Table 1 to produce block polymers. Intermediates 2 and 3 were produced, and block copolymers B and C were produced in the same manner as in Production Example 1, except that the mass ratio of AIBN in producing the block copolymer was changed.
In Production Example 4, block polymer intermediate 2 was produced in the same manner as in Production Example 2, except that the mass ratio of block polymer intermediate 2 and Silaplane FM-0711 was changed to the mass ratio shown in Table 1. A block copolymer D was produced in the same manner as in Production Example 2.

(Comparative Production Example 1: Production of graft copolymer A)
A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer and a digital thermometer was charged with 10 g of ethyl acetate and heated to 75° C. with stirring under a stream of nitrogen. 7.88 g of n-BMA, 1.13 g of HEMA, 2.25 g of Silaplane FM-0711 (mass ratio (nBMA + HEMA) / Silaplane = 80/20), 2,2'-azobis(2,4-dimethyl Valeronitrile) (V-65) and a mixed solution of 7 g of ethyl acetate were added dropwise over 0.5 hours, and after heating and stirring for 5 hours, 0.015 g of V-65 and 0.5 g of ethyl acetate were added. The mixed liquid was added dropwise over 5 minutes and further stirred at the same temperature for 1 hour to obtain a 60% by mass solution of graft copolymer A. As a result of GPC measurement, the resulting graft copolymer A had Mw: 14,000, Mn: 12,000, and PDI: 2.0.

(Example 1)
(1) Preparation of adhesive composition (meth) acrylic acid ester polymer (trade name: SK Dyne 1811L, manufactured by Soken Chemical) 46.5 parts by mass, energy ray-curable polyfunctional compound (trade name: urethane acrylate U- 10PA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 46.5 parts by mass, energy ray initiator (trade name: Irgacure 907, manufactured by BASF) 1.4 parts by mass, block copolymer A of Production Example 1 2.8 parts by mass, thermal crosslinking agent (isocyanate cross-linking agent, product name: Coronate L, manufactured by Nippon Polyurethane Industry) 2.8 parts by mass, solvent (product name: KT11, mixed solvent of toluene and methyl ethyl ketone (mass ratio 1:1), manufactured by DIC Graphics) 333 The adhesive composition 1 of Example 1 was obtained by mixing parts by mass.

(2) Production of adhesive sheet The adhesive composition 1 obtained above was applied to a PET substrate (trade name: Lumirror U34 75 μm manufactured by Toray) with an applicator (manufactured by Yoshimitsu Seiki) so that the film thickness after drying was 50 μm. . After heating in an 80° C. oven for 3 minutes, an adhesive layer was obtained. Thereafter, a release PET film (trade name: E7006, manufactured by Toyobo Co., Ltd.) was attached to the adhesive layer with a clean roller to produce Adhesive Sheet 1 .

(Examples 2-4)
(1) Preparation of adhesive composition In (1) of Example 1, block copolymer A of Production Example 1 was changed to block copolymers B to D of Production Examples 2 to 4, respectively. Adhesive compositions 2 to 4 were obtained in the same manner as in 1 (1).

(2) Production of adhesive sheet In the same manner as in (2) of Example 1, except that the adhesive composition 1 was changed to the adhesive compositions 2 to 4 in (2) of Example 1, Examples 2 to 2 4 adhesive sheets 2 to 4 were obtained.

(Comparative example 1)
(1) Preparation of comparative adhesive composition In the same manner as in Example 1, except that the block copolymer of the present disclosure was not added and the content ratio of other components was changed as shown in Table 2, Comparative An adhesive composition 1 was obtained.

(2) Production of Comparative PSA Sheet Comparative Example 1 was compared in the same manner as in (2) of Example 1, except that PSA composition 1 was changed to comparative PSA composition 1 in (2) of Example 1. An adhesive sheet 1 was obtained.

(Comparative example 2)
(1) Preparation of comparative adhesive composition Same as Example 1, except that block copolymer A of Production Example 1 was changed to graft copolymer A of Comparative Production Example 1 in (1) of Example 1. to obtain a comparative adhesive composition 2.

(2) Production of Comparative PSA Sheet Comparative Example 2 is compared in the same manner as in (2) of Example 1, except that PSA composition 1 is changed to comparative PSA composition 2 in (2) of Example 1. An adhesive sheet 2 was obtained.

(Comparative Example 3)
(1) Preparation of Comparative Adhesive Composition In (1) of Example 1, the block copolymer A of Production Example 1 was synthesized using a commercially available polymeric azo polymerization initiator (VPS) with polydimethylsiloxane. Acrylic polymer block copolymer solution (trade name: My Block Wako 101, manufactured by Wako Pure Chemical Industries, polysiloxane unit weight average molecular weight of about 10000, GPC measurement results, Mw: 21900, Mn: 15200, PDI: 1.44 ) was changed to Comparative adhesive composition 3 in the same manner as in Example 1.

(2) Production of Comparative PSA Sheet Comparative Example 3 was compared in the same manner as in (2) of Example 1, except that PSA composition 1 was changed to comparative PSA composition 3 in (2) of Example 1. An adhesive sheet 3 was obtained.

[evaluation]
<Optical performance evaluation>
The haze value of the pressure-sensitive adhesive sheet before UV irradiation was measured according to JIS K-7105 with a haze meter (HM150, manufactured by Murakami Color Research Laboratory).
The total light transmittance of the pressure-sensitive adhesive sheet before UV irradiation was measured using a haze meter (HM150, manufactured by Murakami Color Research Laboratory) in accordance with JIS K7361-1.

<Evaluation of peel strength of adhesive layer>
Cut to a width of 25 mm, the adhesive layer side of the adhesive sheet with the release PET film peeled off is made to reciprocate once on an acrylic plate adherend (trade name: Acrylite L001, manufactured by Mitsubishi Chemical) with a 2 kg roller (manufactured by Tester Sangyo). After sticking, the peel strength before UV irradiation (initial peel strength) was measured after being left for 3 hours under conditions of 23° C. and humidity of about 60%. After that, using a black light (manufactured by Omiya Kogyo Co., Ltd.), ultraviolet (UV) irradiation was performed at an exposure amount of 500 mJ/cm ² , and then the peel strength after UV irradiation was measured.
The peel force was measured using Tensilon (RTF-1150-H, manufactured by A&D) by a 180° tensile test (moving speed 2.4 m/min, peeling angle 180°, 50 mm movement).

(Summary of results)
The pressure-sensitive adhesive sheets of Examples 1 to 4, which were provided with the pressure-sensitive adhesive layer that was the cured product of the pressure-sensitive adhesive composition to which the block copolymer of the present disclosure was added, exhibited a significantly lower peel strength after UV irradiation than in the comparative examples. It was excellent in easy peelability, small in haze, and excellent in transparency.
On the other hand, Comparative Example 2 having an adhesive layer that is a cured product of a comparative adhesive composition in which a graft copolymer containing a conventional organopolysiloxane structure randomly in a side chain is added instead of the block copolymer of the present disclosure With the pressure-sensitive adhesive sheet of No. 2, the decrease in peel strength after UV irradiation was insufficient compared to Examples, and the haze value increased.
In addition, by using a conventional organopolysiloxane-based high-molecular-weight azo initiator, a block copolymer containing organopolysiloxane at the terminal portion of the main chain (My Block Wako 101) is substituted for the block copolymer of the present disclosure. In the pressure-sensitive adhesive sheet of Comparative Example 3, which had the pressure-sensitive adhesive layer which was the cured product of the added comparative pressure-sensitive adhesive composition, My Block Wako 101 was not compatible with the pressure-sensitive adhesive layer and precipitated.

1 Adhesive layer 2 Base material 10 Adhesive sheet 11 Member to be protected 20 Adhesive protection sheet 100 Laminate

Claims (8)

(Meth) an energy ray-curable component containing an acrylic acid ester polymer, an energy ray initiator, an A block containing a structural unit represented by the following general formula (I), and the following general formula (II) and a block copolymer having a B block containing a structural unit ,
The A block contains a monomer-derived structural unit containing one or more selected from the group consisting of a hydroxyl group, an epoxy group, a carboxyl group, and an amino group,
The content ratio of the structural unit represented by the general formula (I) is 70% by mass or more and 100% by mass or less with respect to the total mass of all the structural units of the A block,
The content ratio of the structural unit represented by the general formula (II) is 100% by mass with respect to the total mass of all structural units of the B block,
The total mass of all structural units of the A block is 50% by mass or more and 90% by mass or less with respect to the total mass of all structural units of the block copolymer,
The total mass of all structural units of the B block is 10% by mass or more and 50% by mass or less with respect to the total mass of all structural units of the block copolymer.
adhesive composition.

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is a monovalent hydrocarbon which may have a substituent and which may contain an oxygen atom in the carbon chain. represents the group,
In general formula (II), R ³ is a hydrogen atom or a methyl group, L ¹ is -COO-, -OCO-, -O-, -CONH-, -COS-, or a direct bond, and L ² is - the group consisting of O-, -NH-, -S-, -COO-, -OCO-, -OCONH-, -NHCO-, -CONH-, -NHCONH-, and -Si(R ^La )(R ^Lb )- a divalent group containing a hydrocarbon group having ¹ to 15 carbon atoms which may be substituted with a hydroxyl group, or a ^direct bond ; Each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a group represented by the following general formula (III), and R ^La and R ^Lb each independently represent 1 to represents a 20 monovalent hydrocarbon group or a hydrogen atom, and a is an integer of 1-50; )

(In general formula (III), R ⁹ to R ¹³ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and b is an integer of 0 to 50.) The adhesive composition according to claim 1 , further comprising a thermal cross-linking agent. The adhesive composition according to claim 2 , wherein the thermal cross-linking agent is an isocyanate-based cross-linking agent. Having an adhesive layer and a substrate disposed on one side of the adhesive layer,
The adhesive layer has a characteristic that the adhesive strength decreases from the initial adhesive strength by irradiation with energy rays, and the adhesive layer is a cured product of the adhesive composition according to any one of claims 1 to 3 . adhesive sheet. An adhesive protective sheet, which is the adhesive sheet according to claim 4 . A laminate comprising the adhesive protective sheet according to claim 5 and a member to be protected attached to the adhesive layer side of the adhesive protective sheet. An optical member to which the adhesive protective sheet according to claim 5 is adhered. An electronic member to which the adhesive protective sheet according to claim 5 is adhered.

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