JP2014148624A - Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet-like formed product, production methods therefor, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet-like formed product that are transparent and have both an adequate adhesiveness and a flexibility, production methods therefor, and a display device having said pressure-sensitive adhesive composition or said pressure-sensitive adhesive sheet-like formed product.SOLUTION: There are provided a pressure-sensitive adhesive composition that is produced by carrying out, in a mixed composition comprising 100 pts.mass of (meth)acrylic resin composition (A) comprising (meth)acrylic acid ester polymer (A1) and (meth)acrylic acid ester monomer (α1), 0.08 pts.mass or more and 1.3 pts.mass or less of polyfunctional epoxy compound (B) having 2 or more and 10000 or less of functional groups and 5 pts.mass or more and 20 pts.mass or less of fatty acid ester of polyvalence alcohol polymer (C), at least the polymerization reaction of (meth)acrylic acid ester monomer (α1), a pressure-sensitive adhesive sheet-like formed product that is produced by forming said mixed composition into a sheet-like product and carrying out the polymerization reaction of (meth)acrylic acid ester monomer (α1), production methods therefor, and a display device having said pressure-sensitive adhesive composition or said pressure-sensitive adhesive sheet-like formed product.

Description

  The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet-like molded article, a production method thereof, and a display device provided with the pressure-sensitive adhesive composition or the pressure-sensitive adhesive sheet-like molded article. .

  The image display unit of image providing devices such as liquid crystal display devices, plasma televisions, and projection screens is laminated with a plurality of members for the purpose of making the light (image light) from the light source appropriate and easy for the observer. Configured. In addition to an appropriate adhesive force, high transparency is required for the adhesive that bonds the members constituting the video display unit having such a laminated structure.

  In order to obtain a transparent adhesive, it is conceivable to use a transparent resin such as an acrylic resin. As a technique related to an adhesive using an acrylic resin, for example, Patent Document 1 discloses a pressure-sensitive adhesive composition having a (meth) acrylate polymer and a metal hydroxide, and the (meth) acrylate polymer. Is an ion-crosslinked structure, the metal hydroxide is a metal hydroxide of Group 2 or Group 13 of the periodic table, and the metal hydroxide of 100 parts by weight of the (meth) acrylate polymer. A pressure-sensitive adhesive composition having a blending ratio of 50 to 200 parts by weight is disclosed.

JP 2002-322447 A

  However, like the technique disclosed in Patent Document 1, an adhesive to which a colored filler is added is unsuitable for applications requiring high transparency. Further, in the prior art, it is difficult to achieve both tensile strength and flexibility in addition to high transparency.

  Therefore, the present invention provides a transparent pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet-like molded article that have both appropriate tensile strength and flexibility, a method for producing them, and the pressure-sensitive adhesive composition or It is an object of the present invention to provide a display device including the pressure-sensitive adhesive sheet-like molded body.

  In the first aspect of the present invention, 100 parts by mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1) 0.08 to 1.3 parts by mass of a polyfunctional epoxy compound (B) having 2 to 10,000 functional groups and 5 to 20 parts by mass of a fatty acid ester (C) of a polyhydric alcohol polymer A pressure-sensitive adhesive composition (F) in which a polymerization reaction of at least the (meth) acrylic acid ester monomer (α1) is performed in a mixed composition comprising:

  In this specification, “(meth) acryl” means “acryl and / or methacryl”. The “polymerization reaction of (meth) acrylate monomer (α1)” means a polymerization reaction for obtaining a polymer containing a structural unit derived from (meth) acrylate monomer (α1).

  In the second aspect of the present invention, 100 parts by mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1) 0.08 to 1.3 parts by mass of a polyfunctional epoxy compound (B) having 2 to 10,000 functional groups and 5 to 20 parts by mass of a fatty acid ester (C) of a polyhydric alcohol polymer The polymerization composition of at least the (meth) acrylic acid ester monomer (α1) is carried out after forming a mixed composition containing the following into a sheet or while forming the mixed composition into a sheet It is a pressure-sensitive adhesive sheet-like molded body (G).

  In the third aspect of the present invention, 100 parts by mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1) 0.08 to 1.3 parts by mass of a polyfunctional epoxy compound (B) having 2 to 10,000 functional groups and 5 to 20 parts by mass of a fatty acid ester (C) of a polyhydric alcohol polymer A pressure-sensitive adhesive composition comprising: a step of producing a mixed composition comprising: and a step of performing a polymerization reaction of at least the (meth) acrylate monomer (α1) in the mixed composition. It is a manufacturing method of a thing (F).

  The 4th aspect of this invention is 100 mass parts of (meth) acrylic resin compositions (A) containing the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer (α1). 0.08 to 1.3 parts by mass of a polyfunctional epoxy compound (B) having 2 to 10,000 functional groups and 5 to 20 parts by mass of a fatty acid ester (C) of a polyhydric alcohol polymer And a step of preparing a mixed composition comprising: and after forming the mixed composition into a sheet shape or while forming the mixed composition into a sheet shape, at least a (meth) acrylate ester It is a manufacturing method of a pressure-sensitive-adhesive sheet-like molded object (G) including the process of performing the polymerization reaction of a body ((alpha) 1).

  The fifth aspect of the present invention is the pressure-sensitive adhesive composition (F) according to the first aspect of the present invention or the pressure-sensitive adhesive sheet-like molded body (G) according to the second aspect of the present invention. Is a display device.

  According to the present invention, a transparent pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet-like molded article having both appropriate tensile strength and flexibility, a method for producing these, and the pressure-sensitive adhesive composition or A display device including the pressure-sensitive adhesive sheet-like molded body can be provided.

1. Pressure-sensitive adhesive composition (F) and pressure-sensitive adhesive sheet-like molded body (G)
The pressure-sensitive adhesive composition (F) of the present invention comprises a (meth) acrylic resin composition (A) containing a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer (α1). A polyfunctional epoxy compound (B) having a functional group of 2 or more and 10,000 or less (hereinafter sometimes simply referred to as “polyfunctional epoxy compound (B)”), and a fatty acid ester (C) of a polyhydric alcohol polymer (C) ( Hereinafter, in a mixed composition containing “modifier (C)”), a polymerization reaction of at least the (meth) acrylate monomer (α1) is performed. . Further, in the above mixed composition, the cross-linking reaction of the polymer of the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1) with the polyfunctional epoxy compound (B). What is performed is preferable.
In addition, "(meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) polymer crosslinking reaction" means (meth) acrylic acid ester polymer (A1). Cross-linking reaction between polymers, cross-linking reaction between polymers containing structural units derived from (meth) acrylic acid ester monomer (α1), and (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester Among the crosslinking reactions with the polymer containing the structural unit derived from the monomer (α1), it means one or a plurality of crosslinking reactions (hereinafter the same).
In addition, the pressure-sensitive adhesive sheet-like molded product (G) of the present invention comprises at least a (meth) acrylic acid ester after the mixed composition is formed into a sheet or while the mixed composition is formed into a sheet. The polymerization reaction of the monomer (α1) is performed. Further, in the above mixed composition, the cross-linking reaction of the polymer of the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1) with the polyfunctional epoxy compound (B). What is performed is preferable.
The substances constituting the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G) will be described below.

<(Meth) acrylic resin composition (A)>
The (meth) acrylic resin composition (A) used in the present invention contains a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer (α1). In addition, when obtaining a pressure sensitive adhesive composition (F) and a pressure sensitive adhesive sheet-like molded object (G), the polymerization reaction of at least (meth) acrylic acid ester monomer (α1) as described above. Done. By performing the polymerization reaction, the polymer containing the structural unit derived from the (meth) acrylate monomer (α1) is mixed and / or partially bonded to the component of the (meth) acrylate polymer (A1). .

  In the present invention, the amount of the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer (α1) used is (mass) acrylic resin composition (A) being 100% by mass, The (meth) acrylic acid ester polymer (A1) is preferably 50% by mass or more and 80% by mass or less, and the (meth) acrylic acid ester monomer (α1) is preferably 20% by mass or more and 50% by mass or less. More preferably, the acrylic acid ester polymer (A1) is 55% by mass or more and 75% by mass or less, and the (meth) acrylic acid ester monomer (α1) is 25% by mass or more and 45% by mass or less. By setting the content ratio of the (meth) acrylic acid ester monomer (α1) in the above range, it is easy to mold the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G). become. The components contained in the (meth) acrylic resin composition (A) will be described in more detail below.

((Meth) acrylic acid ester polymer (A1))
The (meth) acrylic acid ester polymer (A1) that can be used in the present invention is not particularly limited, but the (meth) acrylic acid ester monomer that forms a homopolymer having a glass transition temperature of −20 ° C. or lower. It is preferable to contain the unit (a1) and the monomer unit (a2) having an organic acid group.

  The (meth) acrylate monomer (a1m) that gives the unit (a1) of the (meth) acrylate monomer is not particularly limited. For example, ethyl acrylate (the glass transition temperature of the homopolymer is -24 ° C), n-propyl acrylate (-37 ° C), n-butyl acrylate (-54 ° C), sec-butyl acrylate (-22 ° C), n-heptyl acrylate (-60) ° C), n-hexyl acrylate (-61 ° C), n-octyl acrylate (-65 ° C), 2-ethylhexyl acrylate (-50 ° C), 2-methoxyethyl acrylate (-50 ° C) ), 3-methoxypropyl acrylate (-75 ° C), 3-methoxybutyl acrylate (-56 ° C), ethoxymethyl acrylate (-50 ° C), n-octyl methacrylate (- 5 ° C.), and the like methacrylic acid n- decyl (the -49 ° C.). Among these, n-butyl acrylate, 2-ethylhexyl acrylate, and 2-methoxyethyl acrylate are preferable, n-butyl acrylate and 2-ethylhexyl acrylate are more preferable, and 2-ethylhexyl acrylate is more preferable.

  These (meth) acrylic acid ester monomers (a1m) may be used individually by 1 type, and may use 2 or more types together.

  In the (meth) acrylic acid ester monomer (a1m), the monomer unit (a1) derived therefrom is preferably 80% by mass or more and 99.9% by mass in the (meth) acrylic acid ester polymer (A1). Hereinafter, it is used for polymerization in such an amount that it is more preferably 85% by mass or more and 99.5% by mass or less. When the amount of the (meth) acrylic acid ester monomer (a1m) is within the above range, the viscosity of the polymerization system at the time of polymerization can be easily maintained within an appropriate range.

  Next, the monomer unit (a2) having an organic acid group will be described. The monomer (a2m) that gives the monomer unit (a2) having an organic acid group is not particularly limited, but representative examples thereof include organic acid groups such as a carboxyl group, an acid anhydride group, and a sulfonic acid group. The monomer which has can be mentioned. In addition to these, monomers containing sulfenic acid groups, sulfinic acid groups, phosphoric acid groups, and the like can also be used.

  Specific examples of the monomer having a carboxyl group include, for example, α, β-ethylenically unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, and crotonic acid, and α, In addition to β-ethylenically unsaturated polyvalent carboxylic acid, α, β-ethylenically unsaturated polyvalent carboxylic acid partial esters such as monomethyl itaconate, monobutyl maleate and monopropyl fumarate can be used. Moreover, what has group which can be induced | guided | derived to a carboxyl group by hydrolysis etc., such as maleic anhydride and itaconic anhydride, can be used similarly.

  Specific examples of the monomer having a sulfonic acid group include allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, α, β-unsaturated sulfonic acid such as acrylamide-2-methylpropane sulfonic acid, And salts thereof.

  As the monomer (a2m), among the monomers having an organic acid group exemplified above, a monomer having a carboxyl group is more preferable, and a monomer having acrylic acid or methacrylic acid is particularly preferable. . These monomers are industrially inexpensive and can be easily obtained, have good copolymerizability with other monomer components, and are preferable in terms of productivity. In addition, a monomer (a2m) may be used individually by 1 type, and may use 2 or more types together.

  In the monomer (a2m) having an organic acid group, the monomer unit (a2) derived from the monomer unit (a2) is preferably 0.1% by mass or more and 20% by mass or less in the (meth) acrylic acid ester polymer (A1). More preferably, it is used for the polymerization in such an amount that it is 0.5 to 15% by mass. When the usage-amount of the monomer (a2m) which has an organic acid group exists in the said range, it will become easy to maintain the viscosity of the polymerization system at the time of superposition | polymerization in an appropriate range.

  The monomer unit (a2) having an organic acid group is introduced into the (meth) acrylic acid ester polymer (A1) by polymerization of the monomer (a2m) having an organic acid group as described above. Although it is simple and preferable to perform, an organic acid group may be introduced by a known polymer reaction after the (meth) acrylic acid ester polymer (A1) is formed.

  The (meth) acrylic acid ester polymer (A1) may contain a monomer unit (a3) derived from a monomer (a3m) having a functional group other than an organic acid group. Examples of the functional group other than the organic acid group include a hydroxyl group, an amino group, an amide group, an epoxy group, and a mercapto group.

  Examples of the monomer having a hydroxyl group include (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 3-hydroxypropyl.

  Examples of the monomer having an amino group include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and aminostyrene.

  Examples of monomers having an amide group include α, β-ethylenically unsaturated carboxylic acid amide monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N, N-dimethylacrylamide. Can be mentioned.

  Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and allyl glycidyl ether.

  As the monomer (a3m) having a functional group other than the organic acid group, one type may be used alone, or two or more types may be used in combination.

  In the monomer (a3m) having a functional group other than these organic acid groups, the monomer unit (a3) derived therefrom is 10% by mass or less in the (meth) acrylate polymer (A1). It is preferable to use it for polymerization in such an amount. By using the monomer (a3m) of 10% by mass or less, it becomes easy to keep the viscosity of the polymerization system during polymerization in an appropriate range.

  The (meth) acrylic acid ester polymer (A1) has a (meth) acrylic acid ester monomer unit (a1) that forms a homopolymer having the above-described glass transition temperature of −20 ° C. or lower, and an organic acid group. In addition to the monomer unit (a2) and the monomer unit (a3) having a functional group other than an organic acid group, a monomer derived from the monomer (a4m) copolymerizable with the above-described monomer. The monomer unit (a4) may be contained.

  The monomer (a4m) is not particularly limited, and specific examples thereof include (meth) acrylate monomers other than the (meth) acrylate monomer (a1m), α, β-ethylenic monomers. Saturated polycarboxylic acid complete ester, alkenyl aromatic monomer, conjugated diene monomer, non-conjugated diene monomer, vinyl cyanide monomer, carboxylic acid unsaturated alcohol ester, olefin monomer, etc. Can be mentioned.

  Specific examples of the (meth) acrylate monomer other than the (meth) acrylate monomer (a1m) include methyl acrylate (homopolymer having a glass transition temperature of 10 ° C.), methyl methacrylate. (105 ° C.), ethyl methacrylate (63 ° C.), n-propyl methacrylate (25 ° C.), and n-butyl methacrylate (20 ° C.).

  Specific examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid complete ester include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate and the like.

  Specific examples of the alkenyl aromatic monomer include styrene, α-methylstyrene, methyl α-methylstyrene, vinyl toluene, and divinylbenzene.

  Specific examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (synonymous with isoprene), 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. , 2-chloro-1,3-butadiene, cyclopentadiene, and the like.

  Specific examples of the non-conjugated diene monomer include 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene and the like.

  Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like.

  Specific examples of the carboxylic acid unsaturated alcohol ester monomer include vinyl acetate.

  Specific examples of the olefin monomer include ethylene, propylene, butene, pentene and the like.

  A monomer (a4m) may be used individually by 1 type, and may use 2 or more types together.

  In the monomer (a4m), the amount of the monomer unit (a4) derived therefrom is preferably 10% by mass or less, more preferably 5% by mass or less in the (meth) acrylate polymer (A1). It is subjected to polymerization in such an amount.

  The (meth) acrylic acid ester polymer (A1) has a (meth) acrylic acid ester monomer (a1m) and an organic acid group, which form the homopolymer having a glass transition temperature of −20 ° C. or lower. Monomer (a2m), a monomer containing a functional group other than an organic acid group (a3m) used as necessary, and a monomer copolymerizable with these monomers used as needed It can be particularly suitably obtained by copolymerizing the monomer (a4m).

  The polymerization method for obtaining the (meth) acrylic acid ester polymer (A1) is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, or any other method. . However, among these polymerization methods, solution polymerization is preferable, and among them, solution polymerization using a carboxylic acid ester such as ethyl acetate or ethyl lactate or an aromatic solvent such as benzene, toluene or xylene is more preferable. In the polymerization, the monomer may be added in portions to the polymerization reaction vessel, but it is preferable to add the whole amount at once. The method for initiating the polymerization is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator. The thermal polymerization initiator is not particularly limited, and for example, a peroxide polymerization initiator or an azo compound polymerization initiator can be used.

  Peroxide polymerization initiators include hydroperoxides such as t-butyl hydroperoxide, peroxides such as benzoyl peroxide and cyclohexanone peroxide, and persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. Can be mentioned. These peroxides can also be used as a redox catalyst in appropriate combination with a reducing agent.

  As the azo compound polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) And so on.

  Although the usage-amount of a polymerization initiator is not specifically limited, It is preferable that it is the range of 0.01 to 50 mass parts with respect to 100 mass parts of monomers.

  Other polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers are not particularly limited.

  After completion of the polymerization reaction, the obtained polymer is separated from the polymerization medium as necessary. The separation method is not particularly limited. For example, in the case of solution polymerization, the (meth) acrylic acid ester polymer (A1) can be obtained by placing the polymerization solution under reduced pressure and distilling off the polymerization solvent.

  The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is measured by gel permeation chromatography (GPC method) and is in the range of 100,000 to 1,000,000 in terms of standard polystyrene. Is preferred. The weight average molecular weight of the (meth) acrylic acid ester polymer (A1) can be controlled by appropriately adjusting the amount of the polymerization initiator used in the polymerization and the amount of the chain transfer agent.

  The (meth) acrylic acid ester polymer (A1) is preferably used by mixing two kinds of (meth) acrylic acid ester polymers having different weight average molecular weights (Mw). In this case, by using an appropriate amount of the (meth) acrylic acid ester polymer (A1) having a relatively large weight average molecular weight (Mw), the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G ) To have appropriate tensile strength. On the other hand, by using an appropriate amount of the (meth) acrylic acid ester polymer (A1) having a relatively small weight average molecular weight (Mw), the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded product (G). It becomes easy to give moderate flexibility. That is, by using a mixture of two (meth) acrylic acid ester polymers having different weight average molecular weights (Mw), a pressure-sensitive adhesive composition (F) and a pressure-sensitive adhesive sheet-like molded product (G) are used. It is easy to achieve both moderate tensile strength and flexibility.

  In this case, the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) having a relatively large weight average molecular weight (Mw) is preferably from 500,000 to 1,000,000, and the weight average molecular weight (Mw) is relatively high. The weight average molecular weight (Mw) of the small (meth) acrylic acid ester polymer (A1) is preferably 100,000 or more and less than 500,000. Further, the content ratio of the two is such that the (meth) acrylic acid ester polymer (A1) is 100% by mass, and the (meth) acrylic acid ester polymer (A1) has a relatively large weight average molecular weight (Mw). It is preferable that the (meth) acrylic acid ester polymer (A1) having a relatively small weight average molecular weight (Mw) is 65 to 85% by mass.

  The (meth) acrylic acid ester polymer (A1) may be a mixture of three or more (meth) acrylic acid ester polymers having different weight average molecular weights (Mw).

((Meth) acrylic acid ester monomer (α1))
The (meth) acrylate monomer (α1) is not particularly limited as long as it contains a (meth) acrylate monomer, but forms a homopolymer having a glass transition temperature of −20 ° C. or lower. It is preferable to contain the (meth) acrylic acid ester monomer (a5m).

  As an example of the (meth) acrylic acid ester monomer (a5m) that forms a homopolymer having a glass transition temperature of −20 ° C. or lower, it is used for the synthesis of a (meth) acrylic acid ester polymer (A1) (meta ) The same (meth) acrylate monomer as the acrylate monomer (a1m) can be mentioned. A (meth) acrylic acid ester monomer (a5m) may be used individually by 1 type, and may use 2 or more types together.

  The ratio of the (meth) acrylate monomer (a5m) in the (meth) acrylate monomer (α1) is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass. It is as follows. By making the ratio of the (meth) acrylic acid ester monomer (a5m) in the (meth) acrylic acid ester monomer (α1) within the above range, a pressure-sensitive adhesive composition excellent in pressure-sensitive adhesiveness and flexibility. It becomes easy to obtain a thing (F) and a pressure-sensitive-adhesive sheet-like molded object (G).

  The (meth) acrylic acid ester monomer (α1) is a (meth) acrylic acid ester monomer (a5m) that forms a homopolymer having a glass transition temperature of −20 ° C. or lower. It is good also as a mixture of the monomer (a6m) which has a polymerizable organic acid group.

  Examples of the monomer (a6m) include monomers having an organic acid group similar to those exemplified as the monomer (a2m) used for the synthesis of the (meth) acrylic acid ester polymer (A1). be able to. A monomer (a6m) may be used individually by 1 type, and may use 2 or more types together.

  The ratio of the monomer (a6m) in the (meth) acrylic acid ester monomer (α1) is preferably 30% by mass or less, and more preferably 10% by mass or less. By adjusting the ratio of the monomer (a6m) in the (meth) acrylic acid ester monomer (α1) to the above range, the pressure-sensitive adhesive composition (F) and the feeling excellent in pressure-sensitive adhesiveness and flexibility. It becomes easy to obtain a pressure-adhesive sheet-like molded body (G).

  The (meth) acrylic acid ester monomer (α1), in addition to the (meth) acrylic acid ester monomer (a5m) and the monomer (a6m) having an organic acid group that can be optionally copolymerized, It is good also as a mixture containing the monomer (a7m) copolymerizable with these.

  Examples of the monomer (a7m) include the monomer (a3m) used for the synthesis of the (meth) acrylic acid ester polymer (A1) and the same amount as those exemplified as the monomer (a4m). The body can be mentioned. A monomer (a7m) may be used individually by 1 type, and may use 2 or more types together.

  The ratio of the monomer (a7m) in the (meth) acrylic acid ester monomer (α1) is preferably 20% by mass or less, and more preferably 15% by mass or less.

<Polyfunctional epoxy compound (B)>
Next, the polyfunctional epoxy compound (B) will be described. The polyfunctional epoxy compound (B) is a polyfunctional epoxy compound having 2 to 10,000 functional groups. The polyfunctional epoxy compound (B) can react with the organic acid group in the (meth) acrylic acid ester polymer (A1) to form a crosslinked structure. Similarly, when the (meth) acrylate monomer (α1) contains a monomer having an organic acid group, it can react with the organic acid group. A crosslinked structure can be formed in the polymer containing the structural unit derived from the monomer (α1). Using such a polyfunctional epoxy compound (B), intramolecular and / or intermolecular crosslinking is introduced into the copolymer, so that a pressure-sensitive adhesive composition (F) and a pressure-sensitive adhesive sheet-like molded body (G ) To improve the tensile strength.

  The polyfunctional epoxy compound (B) that can be used in the present invention preferably has a viscosity at 25 ° C. of 600 mPa · s or less, more preferably 500 mPa · s or less, and 400 mPa · s or less. Further preferred. By adjusting the viscosity of the polyfunctional epoxy compound (B) to the above range, the polyfunctional epoxy compound (B) is multifunctional in the mixed composition which is a precursor of the pressure sensitive adhesive composition (F) and the pressure sensitive adhesive sheet-like molded body (G). It is considered that the epoxy compound (B) is easily dispersed uniformly, and the cross-linked structure by the polyfunctional epoxy compound (B) is easily formed uniformly. In addition, the viscosity of a polyfunctional epoxy compound (B) means what was measured as demonstrated below.

(Viscosity measurement method)
Using a B-type viscometer (Tokyo Keiki Co., Ltd.), the following procedure is performed.
(1) Weigh 300 ml of the measurement object in a room temperature environment and place it in a 500 ml container.
(2) Stirring rotor No. Select one from 1, 2, 3, 4, 5, 6, and 7 and attach to the viscometer.
(3) The container containing the measurement object is placed on the viscometer, and the rotor is submerged in the measurement object in the container. At this time, the dent which becomes the mark of the rotor is submerged so as to be exactly at the liquid interface to be measured.
(4) The rotation speed is selected from 20, 10, 4, and 2.
(5) Turn on the stirring switch and read the value after 1 minute.
(6) The value obtained by multiplying the read numerical value by the coefficient A is the viscosity [mPa · s].
The coefficient A is the selected rotor No. as shown in Table 1 below. And the number of revolutions.

  Moreover, the polyfunctional epoxy compound (B) which can be used for this invention has 2 or more and 10,000 or less functional groups, and it is preferable that the number of functional groups is 2 or more and 1000 or less, and is 2 or more and 10 or less. More preferably. When the number of functional groups of the polyfunctional epoxy compound (B) is within the above range, the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G) can be easily provided with appropriate tensile strength. Become.

  Specific examples of the polyfunctional epoxy compound (B) that can be used in the present invention include resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenation Bisphenol A diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, diglycerol tetraglycidyl ether, polyglycerol polyglycidyl ether, sorbitol poly Examples thereof include glycidyl ether. Among them, pentaerythritol tetraglycidyl ether is preferable because a crosslinked structure can be effectively formed even in a small amount. A polyfunctional epoxy compound (B) may be used individually by 1 type, and may use 2 or more types together.

  The amount of the polyfunctional epoxy compound (B) used is 0.08 parts by mass or more and 1.3 parts by mass or less, and 0.08 parts by mass or more and 1 or more by using 100 parts by mass of the (meth) acrylic resin composition (A). It is preferably 0.0 part by mass or less, and more preferably 0.1 part by mass or more and 0.8 part by mass or less. By setting the amount of the polyfunctional epoxy compound (B) used in the above range, the tensile strength appropriate for the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G) as a pressure-sensitive adhesive is obtained. And it becomes easy to give flexibility.

<Polymerization initiator>
When obtaining the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G), the components contained in the (meth) acrylic resin composition (A) are polymerized as described above. In order to accelerate the polymerization reaction, it is preferable to use a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator, an azo thermal polymerization initiator, and an organic peroxide thermal polymerization initiator. However, from the viewpoint of imparting strong adhesive force to the resulting pressure-sensitive adhesive composition (F) and pressure-sensitive adhesive sheet-like molded body (G), it is possible to use an organic peroxide thermal polymerization initiator. preferable.

  Various known photopolymerization initiators can be used as the photopolymerization initiator. Of these, acylphosphine oxide compounds are preferred. Examples of the acylphosphine oxide compound that is a preferred photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  As the azo thermal polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) ) And the like.

  Examples of the organic peroxide thermal polymerization initiator include hydroperoxide such as t-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis ( and a peroxide such as t-butylperoxy) -3,3,5-trimethylcyclohexanone. However, those that do not release volatile substances that cause odor during thermal decomposition are preferred. Among organic peroxide thermal polymerization initiators, those having a 1-minute half-life temperature of 100 ° C. or more and 170 ° C. or less are preferable.

  The amount of the polymerization initiator used is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.1 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). More preferably, it is 0.15 mass part or more and 2 mass parts or less. By making the usage-amount of a polymerization initiator into the said range, it becomes easy to make the polymerization conversion rate of a (meth) acrylic acid ester monomer ((alpha) 1) into an appropriate range, and a pressure sensitive adhesive composition (F) and a pressure sensitive It becomes easy to prevent the monomer odor from remaining in the adhesive sheet-like molded body (G). The polymerization conversion rate of the (meth) acrylic acid ester monomer (α1) is preferably 95% by mass or more. If the polymerization conversion rate of the (meth) acrylic acid ester monomer (α1) is 95% by mass or more, the monomer odor is added to the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded product (G). It is easy to prevent the remaining. In addition, by setting the amount of the polymerization initiator used within the above range, the polymerization reaction proceeds excessively, and the pressure-sensitive adhesive sheet-like molded product (G) does not become a smooth sheet, causing material destruction. It becomes easy to prevent.

<Modifier (C)>
Next, the modifier (C) will be described. The modifier (C) used in the present invention is a fatty acid ester of a polyhydric alcohol polymer. The inventors of the present invention added a proper amount of a predetermined modifier (C) to each of the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G), thereby forming a pressure-sensitive adhesive composition. It has been found that the flexibility of (F) and the pressure-sensitive adhesive sheet-like molded body (G) can be improved.

  Examples of the modifier (C) used in the present invention, that is, the fatty acid ester of the polyhydric alcohol polymer include polyglycerin fatty acid ester, polysorbitan fatty acid ester, polypropylene glycol fatty acid ester and the like. Of these, polyglycerol fatty acid esters are preferred.

Examples of the polyglycerin fatty acid ester include polyglycerin condensed ricinoleic acid ester, polyglycerin ricinoleic acid ester, polyglycerin oleic acid ester, polyglycerin stearic acid ester, and the like. Among them, polyglycerin condensed ricinoleic acid ester is particularly preferable.
Examples of the polysorbitan fatty acid ester include polysorbitan condensed ricinoleic acid ester, polysorbitan ricinoleic acid ester, polysorbitan oleic acid ester, polysorbitan stearic acid ester, and the like.
Examples of the polypropylene glycol fatty acid ester include polypropylene glycol condensed ricinoleic acid ester, polypropylene glycol ricinoleic acid ester, polypropylene glycol oleic acid ester, and polypropylene glycol stearic acid ester.

  Note that ricinoleic acid is a compound having both a carboxyl group and a hydroxyl group. This is referred to as “condensed ricinoleic acid”. The polyglycerin condensed ricinoleic acid ester is obtained by an esterification reaction between a carboxyl group in condensed ricinoleic acid and a hydroxyl group in a compound having a hydroxyl group.

  As the modifier (C), those having a number average molecular weight of 1,000 to 10,000 are preferable. Moreover, it is preferable that a modifier (C) is a liquid under the temperature of 10 to 40 degreeC.

  The amount of the modifier (C) used in the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G) of the present invention is 100 masses of the (meth) acrylic resin composition (A). Part is 5 parts by mass or more and 20 parts by mass or less, preferably 6 parts by mass or more and 18 parts by mass or less, and more preferably 7 parts by mass or more and 15 parts by mass or less. When the content of the modifier (C) exceeds the above range, gelation of the mixed composition which is a precursor of the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G) occurs. The cohesive force of the mixed composition decreases, making it difficult to mold the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G). On the other hand, when the content of the modifier (C) is less than the above range, the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded product (G) are obtained by using the modifier (C). There is a possibility that the effect of improving the flexibility is insufficient.

<Performance>
The pressure-sensitive adhesive composition (F) and pressure-sensitive adhesive sheet-like molded body (G) of the present invention are mainly composed of a transparent (meth) acrylic resin composition (A) and have an appropriate adhesive strength. ing. Moreover, since the pressure sensitive adhesive composition (F) of the present invention and the pressure sensitive adhesive sheet-like molded body (G) do not contain the kind and amount of fillers that excessively impair the transparency, the composition has high transparency. . Furthermore, the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded product (G) of the present invention contain the polyfunctional epoxy compound (B) and the modifier (C) in predetermined amounts, respectively. It has both moderate tensile strength and flexibility.

<Additives>
In addition to the substances described above, the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive composition (F) of the present invention described above are included in the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-shaped molded body (G). ) And pressure-sensitive adhesive sheet-like molded product (G) can be added within a range in which various performances can be satisfied. Known additives include: glass fiber; external cross-linking agent; thickener such as acrylic polymer particles; flame retardant such as phosphate ester; and the like; pressure-sensitive adhesive composition (F) and pressure-sensitive adhesive sheet An additive that does not excessively impair the transparency of the shaped article (G) can be mentioned.

<Application>
As described above, the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G) of the present invention have high transparency. Therefore, the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded body (G) of the present invention are suitable for bonding members constituting the display unit of the display device.

2. Manufacturing method Next, the manufacturing method of a pressure sensitive adhesive composition (F) and a pressure sensitive adhesive sheet-like molded object (G) is demonstrated.

The pressure-sensitive adhesive composition (F) of the present invention is prepared by mixing each substance described so far to prepare a mixed composition, and then at least performing a polymerization reaction of the (meth) acrylic acid ester monomer (α1). It can be obtained by doing.
That is, the method for producing the pressure-sensitive adhesive composition (F) of the present invention comprises a (meth) acrylic resin containing a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer (α1). A step of producing a mixed composition comprising the composition (A), the polyfunctional epoxy compound (B), and the modifier (C), and at least a (meth) acrylic acid ester in the mixed composition A step of polymerizing the monomer (α1). Furthermore, a step of performing a crosslinking reaction of the polymer of the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1) with the polyfunctional epoxy compound (B) is included. It is preferable.
In addition, the substance which can be used other than that, the preferable content ratio of each substance, etc. are as above-mentioned, and detailed description is abbreviate | omitted here.

The pressure-sensitive adhesive sheet-like molded product (G) of the present invention is prepared after mixing each of the substances described so far to produce a mixed composition and molding the mixed composition into a sheet, or the mixed composition It can be obtained by performing a polymerization reaction of at least the (meth) acrylic acid ester monomer (α1) while forming the product into a sheet.
That is, the method for producing the pressure-sensitive adhesive sheet-like molded body (G) of the present invention includes (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1). A step of producing a mixed composition comprising an acrylic resin composition (A), a polyfunctional epoxy compound (B), and a modifier (C), and after forming the mixed composition into a sheet, Alternatively, it includes a step of performing a polymerization reaction of at least the (meth) acrylic acid ester monomer (α1) while forming the mixed composition into a sheet shape. Furthermore, a step of performing a crosslinking reaction of the polymer of the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1) with the polyfunctional epoxy compound (B) is included. It is preferable.
In addition, the substance which can be used other than that, the preferable content ratio of each substance, etc. are as above-mentioned, and detailed description is abbreviate | omitted here.

  In the method for producing the pressure-sensitive adhesive composition (F) and the pressure-sensitive adhesive sheet-like molded product (G) of the present invention, it is preferable to heat the polymerization reaction. For the heating, for example, hot air, an electric heater, infrared rays, or the like can be used. The heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylate monomer (α1) proceeds. Although the preferable range of heating temperature changes with kinds etc. of the polymerization initiator to be used, 100 degreeC or more and 200 degrees C or less are preferable, for example, 130 degreeC or more and 180 degrees C or less are more preferable.

  Moreover, in the manufacturing method of the pressure-sensitive-adhesive sheet-like molded object (G) of this invention, the method of shape | molding the said mixed composition in a sheet form is not specifically limited. Suitable methods include, for example, a method of forming a sheet by applying the mixed composition onto a process paper such as a polyester film subjected to a release treatment, and the mixed composition between two release-processed papers. There are a method of forming a sheet by pressing between rolls with a sandwich, and a method of forming the sheet by extruding the mixed composition using an extruder and controlling the thickness through a die at that time. Can be mentioned.

  The thickness of the pressure-sensitive adhesive sheet-like molded product (G) is not particularly limited, but can be 0.05 mm or more and 5 mm or less, preferably 0.08 mm or more and 4.5 mm or less, and preferably 0.1 mm or more. More preferably, it is 4 mm or less. By setting the thickness of the pressure-sensitive adhesive sheet-like molded body (G) to be equal to or lower than the upper limit of the above range, the transparency of the pressure-sensitive adhesive sheet-shaped molded body (G) can be easily increased. Moreover, it becomes easy to handle by setting the thickness of the pressure-sensitive adhesive sheet-like molded body (G) to be not less than the lower limit of the above range.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. The “parts” and “%” used here are based on mass unless otherwise specified.

<Cohesion force>
As will be described later, a pressure-sensitive adhesive sheet-like molded body sandwiched between two release PET films (polyethylene terephthalate film subjected to release treatment; the same applies hereinafter) is produced, and then the release on the upper surface side is performed. The PET film was peeled off. At this time, if an appropriate cohesive force is applied to the pressure-sensitive adhesive sheet-like molded article, the release PET film can be peeled without destroying the pressure-sensitive adhesive sheet-like molded article. The results are shown in Table 2, where “◯” indicates the case where the pressure-sensitive adhesive sheet-shaped molded article was peeled without breaking, and “X” indicates the case where the pressure-sensitive adhesive sheet-shaped molded article was destroyed. In addition, about the thing whose this evaluation result was "x", subsequent evaluation is not performed.

<Transparency>
As will be described later, a pressure-sensitive adhesive sheet-like molded body was produced, and five sheets thereof were stacked and placed on a business card. The results are shown in Table 2 with “◯” when the characters on the business card can be read and “X” when the characters cannot be read.

<Shear adhesive strength>
As described later, a pressure-sensitive adhesive sheet-like molded body sandwiched between two release PET films was prepared, and a test piece cut out into 20 mm × 25 mm was prepared.
One surface of the aluminum plate was cleaned with Kimwipe containing methyl ethyl ketone (MEK), and a test piece was attached to the cleaned surface. At this time, since the test piece is sandwiched between two release PET films, one release PET film is peeled off and bonded to an aluminum plate, and pressed with a pressure roller from the other release PET film (1 cm). 1 reciprocation at a speed of / sec).
Thereafter, the other release PET film was peeled off and a glass plate was attached so as not to bite air, and left at 23 ° C. for 2 hours. Thereafter, a load cell (1 kN) and a jig were set in a tensile tester (Autograph AGS-500 manufactured by Shimadzu Corporation), and fixed with a lower chuck of the tensile tester with the lower part of the glass plate interposed therebetween.
Next, the wire attached to the aluminum plate was hung on the upper hook of a tensile tester, and the glass plate and the aluminum plate were pulled up and down at a tensile speed of 50 mm / min so as to be shifted in the longitudinal direction of the rectangular shape of the test piece. The maximum value of the test force at this time was read, and the shear adhesive force was calculated from the following formula. The results are shown in Table 2.
Shear adhesive force [N / cm ² ] = maximum test force (N) / area of one side of the adhesive surface of the test piece (cm ² )

<Hardness (flexibility)>
After preparing a pressure-sensitive adhesive sheet-like molded body as described later, a plurality of test pieces were prepared by cutting the pressure-sensitive adhesive sheet-like molded body into a size of 30 mm × 50 mm. The release PET film was peeled off from these test pieces, and the surface from which the release PET film was peeled was pulverized using talc. Test pieces were laminated so that the thickness was about 6 mm, and placed on a sample table of a hardness meter (trade name “CL-150”, manufactured by Kobunshi Keiki Co., Ltd., JIS K7312 compliant). Thereafter, the damper was dropped and the hardness was measured. A value 20 seconds after the damper contacted the sample was read as a measured value. The measurement was performed in a 23 ° C. atmosphere. The results are shown in Table 2.

<Preparation of pressure-sensitive adhesive sheet-shaped molded article>
Example 1
A reactor was charged with 100 parts of a monomer mixture consisting of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.015 part 2,2'-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylic acid ester polymer (A1-1). The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-1) was 800,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.5. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.

  A reactor was charged with 100 parts of a monomer mixture composed of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.03 parts 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylic acid ester polymer (A1-2). The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-2) was 270,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 3.1. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.

Next, 35 parts of 2-ethylhexyl acrylate (2EHA) and a polymerization initiator (1,6-bis (t-butylperoxycarbonyloxy) hexane (one-minute half-life temperature is 150 ° C.)) 0.2 Part, 0.1 part of polyfunctional epoxy compound (B) (manufactured by Nagase ChemteX Corporation, DLC-402) and modifier (C) (trade name “Tirabazole H-818”, manufactured by Taiyo Kagaku Co., Ltd.) 10 parts of a number average molecular weight 4000) are weighed by an electronic balance, and these are 15 parts of the (meth) acrylic acid ester polymer (A1-1) and the (meth) acrylic acid ester polymer (A1-2). Mixed with 50 parts.
For the mixing, a thermostatic bath (Viscomate 150III, manufactured by Toki Sangyo Co., Ltd.) and a Hobart mixer (ACM-5LVT type, manufactured by Kodaira Manufacturing Co., Ltd., capacity: 5 L) were used. First, the temperature control of the Hobart container was set to 23 ° C., a vacuum (−0.1 MPaG) was set, the rotation speed scale was set to 3, and the mixture was stirred for 30 minutes. Thereafter, the temperature control of the Hobart container was set to 50 ° C., the vacuum (−0.1 MPaG) was set, the rotation speed scale was set to 3, and the mixture was stirred for 30 minutes to obtain a mixed composition.

  Next, the mixed composition was hung on a release PET film having a thickness of 75 μm, and another release PET film having a thickness of 75 μm was further covered on the mixed composition. The laminate in which the mixed composition was sandwiched between the release PET films was passed between two rolls with the interval adjusted to 500 μm to form the mixed composition into a sheet. Thereafter, the laminate was put into an oven and heated at 120 ° C. for 15 minutes. By this heating step, the (meth) acrylic acid ester monomer is polymerized and almost simultaneously, the (meth) acrylic acid ester polymer (A1-1) and the (meth) acrylic acid ester polymer (A1-2). And the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer was subjected to a crosslinking reaction to obtain a pressure-sensitive adhesive sheet-like molded product (hereinafter simply referred to as “sheet”) (G1). In addition, it was 99.9% when the polymerization conversion rate of the (meth) acrylic acid ester monomer was computed from the amount of residual monomers in a sheet | seat (G1).

(Examples 2 to 4 and Comparative Examples 1 to 7)
The sheet | seat (G2-G4) which concerns on Examples 2-4, and the sheet | seat (GC1-GC7) which concerns on Comparative Examples 1-7 similarly to Example 1 except having changed the mixing | blending of each substance as shown in Table 2 ) Was produced. In Comparative Example 3, a solventless acrylic plasticizer (manufactured by Toa Gosei Co., Ltd., UP-1000) was used instead of the modifier (C), and in Comparative Example 4, an adipic acid type was used instead of the modifier (C). Polyester (manufactured by ADEKA, PN350) was used, and in Comparative Example 7, a polyfunctional monomer (light acrylate PE-4A, manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of the polyfunctional epoxy compound (B).

As shown in Table 2, all the sheets (G1 to G4) according to the examples had appropriate cohesive strength, high transparency, strong shear adhesive strength, and low hardness. From the fact that the shear adhesive strength was high, it was found that the film had a certain tensile strength, and from the fact that the hardness was low, it was found that the film had flexibility. That is, all the sheets (G1 to G4) according to the examples have both appropriate tensile strength and flexibility.
On the other hand, the sheet (GC1) according to Comparative Example 1 in which the modifier (C) was used in a larger amount than the specified amount of the present invention had insufficient cohesive force. The sheet (GC2) according to Comparative Example 2 in which the compounding amount of the modifier (C) was less than the specified amount of the present invention was high in hardness. Sheet (GC3) according to Comparative Example 3 using a solventless acrylic plasticizer instead of the modifier (C) and Sheet according to Comparative Example 4 using adipic acid-based polyester instead of the modifier (C) ( GC4) had low shear adhesion and high hardness. The sheet (GC5) according to Comparative Example 5 in which the blending amount of the polyfunctional epoxy compound (B) was less than the specified amount of the present invention was insufficient in cohesive force. The sheet (GC6) according to Comparative Example 6 in which the blending amount of the polyfunctional epoxy compound (B) was larger than the specified amount of the present invention had low shear adhesive strength and high hardness. The sheet (GC7) according to Comparative Example 7 using a polyfunctional monomer instead of the polyfunctional epoxy compound (B) had insufficient cohesive strength.

Claims (5)

100 parts by weight of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1),
0.08 parts by mass or more and 1.3 parts by mass or less of a polyfunctional epoxy compound (B) having a functional group of 2 or more and 10,000 or less,
5 parts by mass or more and 20 parts by mass or less of the fatty acid ester (C) of the polyhydric alcohol polymer,
A pressure-sensitive adhesive composition (F) in which at least a polymerization reaction of the (meth) acrylic acid ester monomer (α1) is performed in a mixed composition containing 100 parts by weight of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1),
0.08 parts by mass or more and 1.3 parts by mass or less of a polyfunctional epoxy compound (B) having a functional group of 2 or more and 10,000 or less,
5 parts by mass or more and 20 parts by mass or less of the fatty acid ester (C) of the polyhydric alcohol polymer,
Pressure-sensitive after the polymerization reaction of at least the (meth) acrylic acid ester monomer (α1) is performed after forming the mixed composition containing a sheet into a sheet or while forming the mixed composition into a sheet Adhesive sheet-like molded product (G). 100 parts by weight of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1),
0.08 parts by mass or more and 1.3 parts by mass or less of a polyfunctional epoxy compound (B) having a functional group of 2 or more and 10,000 or less,
5 parts by mass or more and 20 parts by mass or less of the fatty acid ester (C) of the polyhydric alcohol polymer,
Producing a mixed composition comprising:
A step of performing a polymerization reaction of at least the (meth) acrylic acid ester monomer (α1) in the mixed composition;
A process for producing a pressure-sensitive adhesive composition (F). 100 parts by weight of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1),
0.08 parts by mass or more and 1.3 parts by mass or less of a polyfunctional epoxy compound (B) having a functional group of 2 or more and 10,000 or less,
5 parts by mass or more and 20 parts by mass or less of the fatty acid ester (C) of the polyhydric alcohol polymer,
Producing a mixed composition comprising:
A step of performing a polymerization reaction of at least the (meth) acrylic acid ester monomer (α1) after forming the mixed composition into a sheet or while forming the mixed composition into a sheet;
The manufacturing method of the pressure-sensitive-adhesive sheet-like molded object (G) containing.   A display device comprising the pressure-sensitive adhesive composition (F) according to claim 1 or the pressure-sensitive adhesive sheet-like molded body (G) according to claim 2.