JP2017066294A - Adhesive composition and adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition capable of providing excellent transparency in photo-setting or the like, and an adhesive sheet using the adhesive composition.SOLUTION: There is provided an adhesive composition or the like containing at least (A) an acrylic acid ester polymer, (B) a photosetting polyfunctional monomer, (C) a macromonomer, (D) a photoinitiator, (E) a thermal crosslinking agent as blending components by blending the (B) component of 0.1 to 50 pts.wt., the (C) component of 0.1 to 20 pts.wt., the (D) component of 0.01 to 10 pts.wt. and the (E) component of 0.01 to 20 pts.wt. based on 100 pts.wt. of the (A) component and having haze as a cured article of a value of 1% or less.SELECTED DRAWING: None

Description

  The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet, and in particular, a pressure-sensitive adhesive composition comprising a predetermined amount of a macromonomer as a monomer component and having excellent transparency when photocured and heat-cured. And, it is related with the adhesive sheet which uses such an adhesive composition.

Conventionally, a liquid crystal display device provided with an optical film is applied to a display area of a desktop computer, a display panel of a personal computer, an in-vehicle liquid crystal display device, a television screen, etc. Applications are widespread.
As the application range of liquid crystal display devices expands, the usage environment has also become severe.
Therefore, it is desired that high adhesive strength between the optical film (polarizing plate, retardation plate, etc.) and the substrate can be obtained over a long period of time so that it can withstand such a use environment. An adhesive mainly composed of a resin is used.

  For example, the alkyl (meth) acrylate is 57 to 98.8% by weight, the functional group-containing monomer is 1 to 20% by weight, has a (meth) acryloyl group, has a glass transition temperature of 40 ° C. or higher, and has a number average molecular weight. The main component is a copolymer of 0.2 to 3% by weight of a macromonomer having a molecular weight of 2000 to 20000 and at least 0 to 20% by weight of another monomer copolymerizable with the alkyl (meth) acrylate. In addition, a pressure-sensitive adhesive for a liquid crystal device, in which the weight average molecular weight of the copolymer is in the range of 500,000 to 2,000,000, and a predetermined amount of a polyfunctional crosslinking agent is also proposed. (For example, refer to Patent Document 1).

  On the other hand, the applicant of the present invention is an adhesive for polarizing plate, characterized in that the storage elastic modulus (G ′) at 23 ° C. is 0.54 to 15 MPa, and the polarizing plate is a liquid crystal glass cell or It is a pressure-sensitive adhesive for polarizing plates used for bonding to a phase difference plate, and is active in a pressure-sensitive adhesive material containing (A) an acrylic copolymer and (B) an active energy ray-curable compound. It is an adhesive for polarizing plates formed by irradiating energy rays, and (A) the acrylic copolymer contains 0.2 to 6.0% by mass of a monomer unit having a crosslinkable functional group in the molecule (meta ) Acrylic ester copolymer, the (meth) acrylic ester copolymer has a weight average molecular weight of 600,000 to 2,000,000, and the content ratio of the component (A) and the component (B) is The viscosity for polarizing plate is 100: 10 to 100: 40 by mass ratio A dressing has been proposed (see, for example, Patent Document 2).

Japanese Patent No. 3557429 (Claims etc.) Japanese Patent No. 4515357 (Claims etc.)

Here, the pressure-sensitive adhesive for a liquid crystal element disclosed in Patent Document 1 contains a predetermined macromonomer in a predetermined amount, and a macromonomer is copolymerized with another monomer to obtain a main polymer. Thus, an adhesive is obtained using the main polymer.
However, when a macromonomer is simply incorporated as a monomer component in polymerization in the main polymer, the solubility of the resulting main polymer tends to deteriorate, and an adhesive using this lowers transparency. There was a problem. In addition, when a macromonomer is simply incorporated, it is difficult to control the polymerization and gelation is likely to occur during the polymerization.
In addition, the disclosed pressure-sensitive adhesive for liquid crystal elements must be used to limit the glass transition temperature of the macromonomer used to a predetermined value or higher, or to limit the number average molecular weight to a value within a predetermined range. There was also a problem that the restrictions on possible macromonomers were large.

Moreover, although the adhesive for polarizing plates disclosed in Patent Document 2 also exhibits good adhesive properties and durability, (A) an acrylic copolymer and ( B) In some cases, the compatibility between the active energy ray-curable compound and the compatibility with the active energy ray-curable compound tends to be insufficient.
Therefore, in the finally obtained pressure-sensitive adhesive for polarizing plate, the haze is likely to increase. For example, depending on the type and ratio of the (B) active energy ray-curable compound, the value may exceed 1.3%. It was also seen.

Therefore, the present inventors made extensive efforts in view of the above circumstances. As a result, (A) an acrylic polymer, (B) a photocurable polyfunctional monomer, (C) a macromonomer, and (D A phase between (A) an acrylic polymer and (B) a photocurable polyfunctional monomer by forming a pressure-sensitive adhesive composition containing a photopolymerization initiator and (E) a thermal crosslinking agent. Even when it is a cured product with good solubility, good transparency (haze etc.) is maintained while maintaining predetermined substrate adhesion (sometimes referred to simply as adhesive properties) and durability. ) Is stably obtained, and the present invention has been completed.
That is, the object of the present invention is to include not only (A) an acrylic polymer but also a predetermined amount of (B) a photocurable polyfunctional monomer, a macromonomer, etc. as a monomer component, whereby photocuring and thermosetting. To provide a pressure-sensitive adhesive composition that provides excellent transparency and adhesion to a substrate, and a pressure-sensitive adhesive sheet using such a pressure-sensitive adhesive composition (cured material). It is in.

According to the present invention, at least (A) an acrylate polymer, (B) a photocurable polyfunctional monomer, (C) a macromonomer, (D) a photopolymerization initiator, ) Thermal crosslinking agent, and the blending amount of the component (B) is 0.1 to 50 parts by weight and the blending amount of the component (C) with respect to 100 parts by weight of the component (A). 0.1 to 20 parts by weight, (D) component content is 0.01 to 10 parts by weight, and (E) component content is 0.01 to 20 parts by weight. A composition is provided that can solve the above-mentioned problems.
That is, by making the pressure-sensitive adhesive composition containing a predetermined blending component in a predetermined ratio, the compatibility between the component (A) and the component (B) becomes good, and each blending component is photocured and cured. When cured by heat to obtain a cured product, good transparency can be stably obtained while maintaining predetermined substrate adhesion and durability.

Moreover, when comprising the adhesive composition of this invention, it is preferable to make the haze of hardened | cured material made into a value of 1% or less measured based on JISK7136: 2000.
Thus, by using it as the adhesive composition used as the hardened | cured material which restrict | limits haze concretely, it can be used suitably also for uses, such as an optical film for which transparency and clearness are further requested | required. it can.

In constituting the pressure-sensitive adhesive composition of the present invention, the (A) component is preferably a (meth) acrylic acid ester polymer derived from at least the following components (a1) to (a2) as a monomer component. .
(A1) Alkyl group (meth) acrylic acid alkyl ester monomer having 1 to 20 carbon atoms: Polymer component having a crosslinkable group in the molecule other than 100 parts by weight (a2) and (a1) Double bond-containing monomer: 0.5 parts by weight or more and 10 parts by weight or less In this way, by limiting the type and blending ratio of the monomer component of the component (A), the cured product containing it is more In addition to obtaining excellent substrate adhesion and cohesion, these properties can be maintained over a long period of time.
That is, after the pressure-sensitive adhesive composition is photocured and then thermally cured, the crosslinkable group of the (meth) acrylic acid ester polymer of the component (A), such as a hydroxy group, and (E) The thermal crosslinking agent can be sufficiently reacted.

In constituting the pressure-sensitive adhesive composition of the present invention, the component (B) is preferably a bifunctional to pentafunctional (meth) acrylate monomer having an average molecular weight of less than 1000.
In this way, by limiting the average molecular weight and type of component (B), a photocuring reaction can be stably caused, and as a result, predetermined cured substrate adhesion and durability can be maintained in the obtained cured product. However, good transparency can be effectively obtained.

In constituting the pressure-sensitive adhesive composition of the present invention, the component (C) is preferably an acrylate macromonomer having a terminal reactive (meth) acryloyl group.
By limiting the type of component (C) in this way, compatibility with component (A) and the like is increased, and thus compatibility between component (A) and component (B) is further increased. In the obtained cured product, good transparency can be effectively obtained while maintaining predetermined substrate adhesion and durability.

In constituting the pressure-sensitive adhesive composition of the present invention, the component (E) is at least one of an isocyanate compound, an epoxy compound, a carbodiimide compound, an amine compound, a metal chelate compound, and an aziridine compound. Preferably there is.
Thus, by restricting the type of component (E), a thermosetting reaction can be caused stably, and in the resulting cured product, while maintaining a predetermined substrate adhesion and durability, Good transparency can be obtained effectively.

Further, in constituting the pressure-sensitive adhesive composition of the present invention, an antistatic agent is included as the component (F), and the blending amount of the antistatic agent is 0.01% with respect to 100 parts by weight of the component (A). It is preferable to set a value of not less than 10 parts by weight.
Thus, by mix | blending a predetermined amount of (F) component, when using for an optical film etc., generation | occurrence | production of the static electricity at the time of the sticking to a to-be-adhered body, or peeling can be prevented effectively.

Moreover, another aspect of the present invention is that on a base material, at least (A) an acrylate polymer, (B) a photocurable polyfunctional monomer, (C) a macromonomer, and (D And (E) a pressure-sensitive adhesive sheet comprising a cross-linked product of a pressure-sensitive adhesive composition containing a photopolymerization initiator, and (E) a thermal cross-linking agent. The blending amount of component (B) is 0.1 to 50 parts by weight, the blending amount of component (C) is 0.1 to 20 parts by weight, the blending amount of component (D) is 0.01 to 10 parts by weight, and (E) It is an adhesive sheet characterized by making the compounding quantity of a component into the value within the range of 0.01-20 weight part.
By constructing the pressure-sensitive adhesive sheet including the predetermined pressure-sensitive adhesive layer in this manner, the compatibility between the component (A) and the component (B) becomes good, and the pressure-sensitive adhesive layer is photocured and heat-cured. In this case, good transparency can be stably obtained while maintaining predetermined substrate adhesion and durability.

[First embodiment]
In the first embodiment of the present invention, at least (A) an acrylate polymer, (B) a photocurable polyfunctional monomer (sometimes referred to as a photocrosslinking agent), and (C) a macro as compounding components. A pressure-sensitive adhesive composition comprising a monomer, (D) a photopolymerization initiator, and (E) a thermal crosslinking agent, wherein the blending amount of component (B) is 0 with respect to 100 parts by weight of component (A). 0.1 to 50 parts by weight, 0.1 to 20 parts by weight of component (C), 0.01 to 10 parts by weight of component (D), and 0 to 10 parts of component (E). The pressure-sensitive adhesive composition is characterized by having a value within the range of 01 to 20 parts by weight.
Hereinafter, the pressure-sensitive adhesive composition according to the first embodiment of the present invention will be specifically described with reference to the drawings as appropriate.

1. (A) Component: Acrylic ester polymer (1) Type 1
About the kind of acrylic acid ester polymer that is the main component of the adhesive, so-called acrylic polymers derived from (meth) acrylic acid ester monomers (homopolymers and copolymers of (meth) acrylic acid ester monomers) Each is included. The same applies hereinafter.) So long as it is not particularly limited, and can be appropriately selected depending on the application.
That is, by changing the type of (meth) acrylic acid ester monomer, blending amount, etc., it is relatively easy to adjust substrate adhesion and cohesive force, and by making an inexpensive acrylic acid ester polymer, The obtained pressure-sensitive adhesive composition can be applied to various uses.

In addition, (A) the acrylate polymer is a monomer component that is at least the following (a1) to (a2) component, or at least the (meth) acrylate ester copolymer derived from the following (a1) to (a3) components: More preferably, it is a coalescence.
(A1) (meth) acrylic acid alkyl ester monomer having 1 to 20 carbon atoms in the alkyl group: 100 parts by weight (a2) Polymerizable double bond-containing monomer having a crosslinkable group in the molecule: 0.5 weight Part or more and 10 parts by weight or less (a3) polymerizable double bond-containing monomer having an aromatic ring in the molecule: 0.1 part by weight or more and 30 parts by weight or less This reason is introduced into the molecule of the acrylate polymer This is because crosslinking is possible by using the hydroxyl group thus formed.
Therefore, the balance between reworkability and durability under a predetermined environment is further improved, and an acrylic pressure-sensitive adhesive composition that is relatively inexpensive and easy to manufacture can be obtained.

(1) -1. Monomer component (a1)
The (A) acrylic acid ester polymer preferably contains a (meth) acrylic acid alkyl ester containing an alkyl group having 1 to 20 carbon atoms as the monomer component (a1) for polymerization.
The reason for this is that when the number of carbon atoms of the alkyl group is larger than 20, the substrate adhesiveness of the resulting pressure-sensitive adhesive composition may decrease due to the orientation and crystallization of the side chains. is there.
Therefore, the lower limit of the carbon number of the alkyl group in the (meth) acrylic acid ester polymer is more preferably 1 or more, and further preferably 4 or more.
Further, the upper limit of the carbon number of the alkyl group is more preferably 10 or less, and further preferably 8 or less.

Examples of the alkyl (meth) acrylate alkyl ester having an alkyl group with a carbon number of 1 or more and 20 or less include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate And one kind or a combination of two or more kinds such as dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like.
Moreover, since monomer component (a1) is a main component which comprises (A) acrylic ester polymer, normally, it is the compounding quantity with respect to all the monomer components (100 weight%) which comprise (A) component. The lower limit is preferably 50% by weight or more, more preferably 60% by weight or more, and still more preferably 85% by weight or more.
Furthermore, the upper limit of the monomer component (a1) is preferably 99.5% by weight or less, more preferably 99% by weight or less, and even more preferably 90% by weight or less. preferable.

(1) -2 Monomer component (a2)
Moreover, it is preferable that (A) acrylic acid ester polymer contains the polymerizable double bond containing compound which has a crosslinkable group in a molecule | numerator as a monomer component (a2) at the time of superposing | polymerizing.
The reason for this is that by including such a monomer component (a2), the crosslinkable group, for example, a hydroxy group, a carboxyl group, an amino group, an amide group, an epoxy group, and the like are crosslinked in the (meth) acrylate polymer. This is because it becomes a sex functional group.
That is, when a cross-linking agent is added to the pressure-sensitive adhesive composition, (A) the acrylic acid ester polymer can be effectively cross-linked via the cross-linkable group, and the cohesive strength of the resulting pressure-sensitive adhesive The adhesion and storage elastic modulus can be easily adjusted.

Examples of the polymerizable double bond-containing compound having a crosslinkable group in the molecule include hydroxyl group-containing vinyl ethers such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexyldimethanol monovinyl ether, allyl alcohol, allyl glycol, and allyl diglycol. Allyl ether of vinyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) (Meth) acrylic acid hydroxyalkyl ester such as 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, etc. It includes a combination of the above.
Moreover, since the compatibility with the (meth) acrylic acid ester monomer which is the main component constituting the (meth) acrylic acid ester polymer is even better, it is more preferable to use a (meth) acrylic acid hydroxyalkyl ester, More preferably, it is either 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate.

In addition, it is also preferable to use acrylic acid and a hydroxy group-containing monomer in combination as a polymerizable double bond-containing compound having a crosslinkable group in the molecule.
The reason for this is that by introducing both functional groups, an effect of promoting the crosslinking reaction between the hydroxy group which is a crosslinkable group and the isocyanate compound as the crosslinking agent is exhibited.
Furthermore, it is because the carboxyl group itself that acrylic acid has reacts with the isocyanate compound.
In addition, when using together acrylic acid and a hydroxyl-group containing monomer as a polymerizable double bond containing compound which has a crosslinkable group in a molecule | numerator, it is 99: 1 to 1:99 regarding the combined use ratio (weight ratio). A value within the range is preferable, a value within the range of 70:30 to 30:70 is more preferable, and a value within the range of 65:35 to 50:50 is more preferable.
That is, when the total amount of both is 100 parts by weight, the lower limit of acrylic acid and hydroxy group-containing monomer is preferably 1 part by weight or more, more preferably 30 parts by weight or more, 35 More preferably, it is at least part by weight.
In terms of the upper limit of acrylic acid and hydroxy group-containing monomer, it is preferably 99 parts by weight or less, more preferably 70 parts by weight or less, and even more preferably 65 parts by weight or less.

Moreover, it is preferable to make the compounding quantity of a monomer component (a2) into the value of 0.5 to 10 weight part with respect to 100 weight part of monomer components (a1).
The reason for this is that when the amount of the monomer component (a2) is less than 0.5 parts by weight, the crosslinking between the components (A) becomes insufficient, and the durability under a predetermined environment may deteriorate. is there.
On the other hand, when the compounding amount of the monomer component (a2) exceeds 10 parts by weight, the base material adhesion may be excessively reduced when the pressure-sensitive adhesive composition is cured.
Therefore, the lower limit of the amount of the monomer component (a2) is more preferably 1 part by weight or more with respect to 100 parts by weight of the monomer component (a1).
The upper limit of the amount of the monomer component (a2) is more preferably 5 parts by weight or less with respect to 100 parts by weight of the monomer component (a1).

(1) -3 Monomer component (a3)
Moreover, although it is an arbitrary monomer component, it is also preferable to use together the polymerizable double bond containing monomer which is monomer components other than (a1) and (a2), and has an aromatic ring in a molecule | numerator.
This is because the refractive index of the resulting pressure-sensitive adhesive composition can be induced to be higher by using the polymerizable double bond-containing monomer (a3) having an aromatic ring in the molecule. This is because leakage can be effectively prevented.
Here, regarding the kind of the polymerizable double bond-containing monomer (a3) having an aromatic ring in the molecule, for example, phenyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate, (meth ) 2-phenoxyethyl acrylate, 2-phenoxybutyl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 1,1′-biphenyl- (meth) acrylate One type alone or a combination of two or more types such as 2-yl, (meth) acrylic acid ethylene oxide-modified cresol, (meth) acrylic acid ethylene oxide-modified nonylphenol can be used.

Moreover, when using together the polymerizable double bond containing monomer (a3) which has an aromatic ring in this molecule | numerator, the said compounding quantity is 0.1 weight part or more normally with respect to 100 weight part of monomer components (a1). The value is preferably 30 parts by weight or less.
This is because if the amount of the monomer component (a3) is less than 0.1 parts by weight, the blending effect may not be exhibited.
On the other hand, when the amount of the monomer component (a3) exceeds 30 parts by weight, the substrate adhesion and transparency when the pressure-sensitive adhesive composition is cured may be excessively lowered.
Therefore, the lower limit of the amount of the monomer component (a3) is more preferably 0.5 parts by weight or more, and more preferably 2 parts by weight or more with respect to 100 parts by weight of the monomer component (a1). Further preferred.
Furthermore, the upper limit of the amount of the monomer component (a3) is more preferably 8 parts by weight or less, and more preferably 5 parts by weight or less with respect to 100 parts by weight of the monomer component (a1). preferable.

(2) Type 2
In addition, as a part of the component (A), a polyurethane polymer, a polyester polymer, a polyolefin polymer, a polycarbonate polymer, a natural rubber, a synthetic rubber, a styrenic thermoplastic elastomer to be used in combination with the acrylate polymer described above. It is also preferable to use at least one of silicone resin, phenol resin and the like.
In particular, if it is a polyurethane polymer etc., it can be set as the adhesive component excellent in elasticity and elasticity as a part of (A) component.
Moreover, if it is a silicone resin, a phenol resin, etc., it can be set as the adhesive component which was further excellent in heat resistance, durability, etc. as a part of (A) component.

(3) Compounding amount Moreover, when the total amount of the pressure-sensitive adhesive composition is 100% by weight, the blending amount (solid content conversion value) of the acrylate polymer as component (A) is 30% by weight or more, The value is preferably 99% by weight or less.
The reason for this is that when the amount of the component (A) is less than 30% by weight, the effect of addition may not be exhibited.
On the other hand, when the blending amount of the component (A) exceeds 99% by weight, reworkability, durability and the like may be significantly reduced.
Therefore, with respect to the lower limit of the amount of component (A), when the total amount of the pressure-sensitive adhesive composition is 100% by weight, it is more preferably 50% by weight or more, and 75% by weight or more. More preferably.
Further, with respect to the upper limit of the amount of component (A), when the total amount of the pressure-sensitive adhesive composition is 100% by weight, it is more preferably 95% by weight or less, and 90% by weight or less. More preferably.

2. (B) Component: Photocurable Polyfunctional Monomer As the component (B), a photocurable polyfunctional monomer (sometimes referred to as a photocrosslinking agent) is blended.
That is, by containing such a photocurable polyfunctional monomer, it is possible to react with the reactive group or the like of the component (A) to increase the molecular weight of the component (A) and thus to three-dimensionally crosslink. .
Therefore, it is possible to easily control the base material adhesion, cohesiveness, and the like when the pressure-sensitive adhesive layer is formed within a desired range.
More specifically, as the component (B), for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, dipentaglycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, Di (meth) acrylate modified with ethylene oxide, di (meth) acryloxyethyl isocyanurate, allylated cyclohexyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dimethylol disi Lopentane 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- Bifunctional polyfunctional (meth) acrylate monomers such as (acryloyloxyethoxy) phenyl] fluorene, 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 s (meth) acryloxyethyl isocyanurate, tetrafunctional types such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate, such as propionic acid-modified di Pentafunctional polyfunctional (meth) such as pentaerythritol penta (meth) acrylate, pentafunctional polyfunctional (meth) acrylate monomers, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, etc. One kind alone or a combination of two or more kinds of acrylate monomers can be mentioned.

In addition, as such a polyfunctional (meth) acrylate monomer as one of the components (B), from the viewpoint of keeping the haze value low, the skeleton structure has a cyclic structure such as a carbocyclic structure and a heterocyclic structure. Or it is preferable to have any one cyclic structure, and it is especially preferable to have a heterocyclic structure.
Examples of such polyfunctional (meth) acrylate monomers include isocyanurate structures such as di (meth) acryloxyethyl isocyanurate, tris (meth) acryloxyethyl isocyanurate, and isocyanuric acid ethylene oxide-modified triacrylate. Polyfunctional (meth) acrylate monomers having dimethylol, dimethylol dicyclopentane di (meth) acrylate, ethylene oxide-modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, neopentyl glycol Modified trimethylolpropane di (meth) acrylate, adamantane di (meth) acrylate and the like are suitable.
Of these, polyfunctional (meth) acrylate monomers having an isocyanurate structure are particularly preferable. In addition, when using a hardening | curing agent, it is also preferable to coexist the polymerization initiator by light or a heat | fever.

(2) Compounding quantity Moreover, the compounding quantity of (B) component shall be the value of 0.1 to 50 weight part with respect to 100 weight part of acrylic ester polymer which is (A) component.
The reason for this is that when the amount of component (B) is less than 0.1 parts by weight, the effect of addition may not be manifested.
On the other hand, when the blending amount of the component (B) exceeds 50 parts by weight, the properties such as storage stability, substrate adhesion, or reworkability of the pressure-sensitive adhesive composition may be significantly reduced. is there.
Accordingly, the lower limit of the amount of component (B) is more preferably 0.5 parts by weight or more, and more preferably 1 part by weight or more with respect to 100 parts by weight of component (A). preferable.
Further, with respect to the upper limit of the blending amount of the component (B), it is more preferably set to a value of 30 parts by weight or less, more preferably 20 parts by weight or less, with respect to 100 parts by weight of the component (A). A value of 10 parts by weight or less is particularly preferable.

3. Component (C): Macromonomer (1) Type The macromonomer of component (C) is a relatively high molecular weight monomer component having a polymerizable functional group at the molecular end or at both ends, and a polymer chain portion and a polymerizable property. And a functional group portion.
Here, the polymerizable functional group is preferably a group having an ethylenically unsaturated double bond (ethylenically unsaturated group).
Specifically, at least one selected from the group consisting of a vinyl group, an allyl group, a (meth) acryloyl group, and a propenyl group is preferable.
On the other hand, the polymer chain part constituting the macromonomer is methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylic acid t. -Main structural units of repeating units derived from (meth) acrylic acid alkyl esters such as butyl, 2-ethylhexyl (meth) acrylate, stearyl acrylate, or styrene, acrylonitrile, hydroxy (meth) acrylate, silicone, etc. It is preferable that the polymer is
Further, from the viewpoint of further improving the compatibility with the component (A), the polymer chain portion is preferably a repeating unit derived from (meth) acrylic acid alkyl ester, and has 4 or more carbon atoms. Particularly preferred is a repeating unit derived from 8 or less (meth) acrylic acid alkyl ester.
These polymer chain portions may be composed of a single repeating unit, or may be composed of a plurality of repeating units, and are also an alternating copolymer, random copolymer, block copolymer. Any of these may be used.

  Therefore, a preferred example of the macromonomer includes a compound represented by the following structural formula (I).

In Structural Formula (I), R ¹ represents a hydrogen atom or a methyl group.
X represents a single bond or a divalent linking group, and examples thereof include a linear, branched or cyclic alkylene group, an aralkylene group, and an arylene group. In the divalent linking group, —NR ² — (R ² : hydrogen or an alkyl group such as a methyl group, an ethyl group, or a propyl group), —COO—, —OCO—, —O—, —S—, —SO ₂ NH—, —NHSO ₂ —, —NHCOO—, —OCONH—, a group derived from a heterocyclic ring, or the like may be interposed as a linking group.
Further, Y represents methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic. (Meth) acrylic acid alkyl esters such as 2-ethylhexyl acid and stearyl acrylate, or homopolymerization or copolymerization of at least one monomer component selected from styrene, acrylonitrile, hydroxy (meth) acrylate, and silicone Represents a polymer chain.

Moreover, it is preferable to make the number average molecular weight (Mn) of a macromonomer into the value of 2000 or more and 20000 or less.
The reason for this is that if the number average molecular weight (Mn) is less than 2000, sufficient adhesiveness and heat resistance may not be obtained when the pressure-sensitive adhesive layer is constituted from the pressure-sensitive adhesive composition.
On the other hand, when the number average molecular weight (Mn) exceeds 20000, the viscosity of the pressure-sensitive adhesive composition is remarkably increased, and accordingly, workability is remarkably decreased, or compatibility of the macromonomer with the component (A) and the like. This is because the reactivity of the polymerizable functional group may be significantly reduced.
Accordingly, the lower limit of the number average molecular weight (Mn) of the macromonomer is more preferably 3000 or more, and even more preferably 4000 or more.
Moreover, it is more preferable to set it as a value of 10,000 or less with respect to the upper limit of the number average molecular weight (Mn) of the macromonomer, and it is more preferable to set it as a value of 8000 or less.
In addition, the number average molecular weight (Mn) of the macromonomer can be measured as a standard polystyrene conversion value by a GPC (gel permeation chromatography) method.

Moreover, it is preferable to make glass transition temperature (Tg) of a macromonomer into the value of -100 degreeC or more and 150 degrees C or less.
The reason for this is that the cohesive force (physical crosslinking effect) due to the microdomains of the macromonomer appears in the temperature range below the glass transition temperature of the macromonomer, and this cohesive force may be significantly reduced near the glass transition temperature. Because.
Therefore, it is preferable to set the glass transition temperature to a value of −100 ° C. or higher from the viewpoint of securing a sufficient cohesive force, and it is preferable to set the temperature to 150 ° C. or lower because it can suppress a decrease in tackiness and adhesive strength. .
Therefore, the lower limit of the glass transition temperature of the macromonomer is more preferably −80 ° C. or more, and further preferably −50 ° C. or more.
Moreover, it is more preferable to set it as the value of 100 degrees C or less about the upper limit of the glass transition temperature of a macromonomer, and it is further more preferable to set it as the value of 0 degrees C or less.

Further, although there is no particular limitation on the method for producing the macromonomer, for example, the following production methods (1) to (3) are suitable. (1) Polymer chain constituting the macromonomer by living anion polymerization (living polymer anion) (2) An oligomer having a carboxyl group at the terminal by polymerizing a radical polymerizable monomer such as methyl methacrylate in the presence of a chain transfer agent such as mercaptoacetic acid. (3) In the presence of an azo polymerization initiator containing a carboxyl group, a radical polymerizable monomer such as methyl methacrylate is polymerized to have a carboxyl group at the terminal. After obtaining an oligomer, a method of making it a macromonomer with glycidyl methacrylate

And a commercial item can also be used as a macromonomer of (C) component.
For example, a macromonomer (product name: 45% AA-6 (AA-6S), AA-6; manufactured by Toagosei Co., Ltd.) whose molecular end is a methacryloyl group and whose polymer chain is polymethyl methacrylate (PMMA), Macromonomer (Product Name: AS-6S, AS-6; manufactured by Toagosei Co., Ltd.) whose polymer chain is polystyrene, Macromonomer (Product Name: AN-6S; whose polymer chain is a styrene / acrylonitrile copolymer) Toagosei Co., Ltd.), a macromonomer whose polymer chain is polybutyl acrylate (product name: AB-6; manufactured by Toagosei Co., Ltd.), and the like can be used.

(2) Compounding quantity Moreover, the compounding quantity of (C) component shall be the value of 0.1 weight part or more and 20 weight part or less with respect to 100 weight part of acrylic ester polymers which are (A) components.
The reason for this is that when the blending amount of the component (C) is less than 0.1 parts by weight, the additive effect for improving compatibility may not be exhibited.
On the other hand, when the blending amount of the component (C) exceeds 20 parts by weight, characteristics such as storage stability, substrate adhesion, and reworkability may be remarkably deteriorated.
Accordingly, the lower limit of the amount of component (C) is more preferably 0.5 parts by weight or more and more preferably 1 part by weight or more with respect to 100 parts by weight of component (A). preferable.
Further, the upper limit of the amount of component (C) is more preferably 20 parts by weight or less, and still more preferably 10 parts by weight or less with respect to 100 parts by weight of component (A).

4). (D) Component: Photopolymerization Initiator (1) Type As the photopolymerization initiator (D) component, any compound that can generate radicals when irradiated with a predetermined amount of radiation such as ultraviolet rays can be used. Are, for example, 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-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -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, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate Acid ester, oligo [2-hydroxy-2-methyl-1 [4- (1-methylvinyl) phenyl] propanone], 2,4,6-trimethylbenzoyl-diphenyl- One kind alone or a combination of two or more kinds such as phosphine oxide may be mentioned.

(2) Compounding quantity Moreover, the compounding quantity of (D) component shall be 0.01 weight part or more and 10 weight part or less with respect to 100 weight part of (A) component.
This is because when the amount of component (D) is less than 0.01 part by weight, the effect of addition does not appear and the photopolymerization reaction may not occur sufficiently.
On the other hand, when the blending amount of the component (D) exceeds 10 parts by weight, characteristics such as storage stability, substrate adhesion, and reworkability may be remarkably deteriorated.
Therefore, the lower limit of the amount of component (D) is more preferably 0.05 parts by weight or more and 100 parts by weight or more with respect to 100 parts by weight of component (A). Is more preferable.
Further, the upper limit of the amount of component (D) is preferably 5 parts by weight or less, and more preferably 3 parts by weight or less with respect to 100 parts by weight of component (A).

5. (E) Component: Thermal Crosslinker (1) Type (E) Component as the thermal crosslinker is an isocyanate compound, an epoxy compound, a carbodiimide compound, an amine compound, a metal chelate compound, and an aziridine compound. It is preferable that it is at least one.
The reason for this is that these thermal crosslinking agents can reliably react with the functional groups and the like of the component (A) in the molecule and form a crosslinked structure even when added in a relatively small amount.
Moreover, among these (E) components, an isocyanate compound is particularly preferable.
The reason for this is that if it is an isocyanate compound, it can react reliably with the functional group or the like of the component (A) even at a relatively low temperature such as room temperature. This is because the haze, gel fraction, and storage elastic modulus (G ′) can be easily adjusted to values within a desired range.

Suitable isocyanate compounds include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. Isocyanates and the like, and biurets, isocyanurates, and adducts that are a reaction product with a low molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. be able to.
More preferable examples include tolylene diisocyanate-modified trimethylolpropane.

(2) Compounding quantity Moreover, the compounding quantity of (E) component shall be the value of 0.01 to 20 weight part with respect to 100 weight part of (A) component.
The reason for this is that when the amount of component (E) is less than 0.01 parts by weight, the effect of addition does not appear and the thermal crosslinking reaction may not occur sufficiently.
On the other hand, when the blending amount of the component (E) exceeds 20 parts by weight, characteristics such as storage stability, substrate adhesion, and reworkability may be remarkably deteriorated.
Accordingly, the lower limit of the amount of component (E) is more preferably 0.05 parts by weight or more and 100 parts by weight or more with respect to 100 parts by weight of component (A). Is more preferable.
Further, the upper limit of the amount of component (E) is more preferably 10 parts by weight or less, still more preferably 4 parts by weight or less, with respect to 100 parts by weight of component (A). A value of 1 part by weight or less is particularly preferable.

6). Component (F): Antistatic agent (1) Type As the antistatic agent as component (F), an alkali metal salt is typical, but in addition, a quaternary ammonium cation, an N-alkylated pyridinium cation, N, Examples thereof include at least one of N′-alkylated imidazolium cation, nitrogen-containing onium salt of any of N, N′-alkylated piperidinium cation, sulfur-containing onium salt, and phosphorus-containing onium salt.
And as a suitable antistatic agent, among alkali metal salts, potassium bis (fluorosulfonyl) imide, potassium bis (perfluoroalkylsulfonyl) imide, potassium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) Imido, lithium bis (perfluoroalkylsulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, tetraalkylammonium bis (fluorosulfonyl) ) Imide, tetraalkylammonium bis (perfluoroalkylsulfonyl) imide, tetraalkylammonium bis (trifluoromethylsulfonyl) imide, tetraalkylammonium hexafluorophosphate Include alone or in combinations of two or more such hexafluorophosphate 1-methyl-4-alkylpyridinium analogues.
This is because an alkali metal salt such as potassium bis (fluorosulfonyl) imide exhibits excellent antistatic properties in a relatively small amount.

(2) Compounding quantity Moreover, the compounding quantity of (F) component shall be 0.01 weight part or more and 10 weight part or less with respect to 100 weight part of (A) component.
This is because when the blending amount of the component (F) is less than 0.01 parts by weight, the effect of addition does not appear and the antistatic effect may not be obtained.
On the other hand, when the blending amount of the component (F) exceeds 10 parts by weight, characteristics such as substrate adhesion or reworkability may be remarkably deteriorated.
Accordingly, the lower limit of the amount of component (F) is more preferably 0.05 parts by weight or more and 100 parts by weight or more with respect to 100 parts by weight of component (A). Is more preferable.
The upper limit of the amount of component (F) is more preferably 7 parts by weight or less, and still more preferably 4 parts by weight or less with respect to 100 parts by weight of component (A).

7). (G) Component: Coupling Agent (1) Type As the component (G), it is preferable to blend a coupling agent, for example, a silane coupling agent.
The reason for this is that when a coupling agent is blended in the pressure-sensitive adhesive composition to form an optical film and bonded to a liquid crystal glass cell or the like, the adhesiveness between the pressure-sensitive adhesive layer and the glass cell. Is a preferred compounding component because it becomes more favorable.
Here, as a suitable coupling agent, vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-chloropropyltri One kind of methoxysilane or a combination of two or more kinds may be mentioned.
Further, together with these coupling agents or separately from these coupling agents, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxy It is also preferable to blend an alkylalkoxysilane such as silane and diphenyldimethoxysilane, and a hydrolytic condensate with allylalkoxysilanes.

(2) Compounding quantity Moreover, it is preferable to make the compounding quantity of (G) component into 0.01 to 10 weight part with respect to 100 weight part of (A) component.
The reason for this is that when the amount of component (G) is less than 0.01 parts by weight, the effect of addition may not be manifested.
On the other hand, when the blending amount of the component (G) exceeds 10 parts by weight, it may be difficult to control the substrate adhesiveness and reworkability of the pressure-sensitive adhesive composition.
Therefore, the lower limit of the amount of component (G) is more preferably 0.05 parts by weight or more and 100 parts by weight or more with respect to 100 parts by weight of component (A). Is more preferable.
Further, the upper limit of the amount of component (G) is more preferably 5 parts by weight or less, still more preferably 3 parts by weight or less with respect to 100 parts by weight of component (A). A value of 1 part by weight or less is particularly preferable.

8). Solvent and other compounding components Moreover, the pressure-sensitive adhesive composition may include other compounding components other than the components (A) to (G) described above.
For example, in order to improve the applicability to a substrate or the like and the mixing property of the compounding components, it is typically preferable to handle it as a pressure-sensitive adhesive composition solution containing a predetermined amount of a solvent.
Here, the type of the solvent is not particularly limited, and examples thereof include esters, aromatic hydrocarbons, ketones, and ethers.
More specifically, since it has good solubility in the component (A) and is easy to handle, methyl acetate, ethyl acetate, n-butyl acetate, i-butyl acetate, benzene, toluene, xylene, acetone , Cyclohexane, cyclohexanone, methyl ethyl ketone, tetrahydrofuran and the like, or a combination of two or more thereof.

Moreover, it is preferable to set it as the value of 5 weight% or more and 40 weight% or less with respect to the whole quantity (100 weight%) of an adhesive composition solution about the compounding quantity of a solvent.
The reason for this is that when the amount of the solvent is less than 5% by weight, the viscosity of the pressure-sensitive adhesive composition solution becomes excessively high, and the applicability to the base material and the mixability of the compounding components may be significantly reduced. Because there is.
On the other hand, when the blending amount of the solvent exceeds 40% by weight, the viscosity of the pressure-sensitive adhesive composition solution is excessively lowered, and similarly, the applicability to the substrate or the like is remarkably reduced, or This is because the blended components may be easily precipitated.
In addition, regarding the compounding quantity of a solvent, the solvent at the time of solution-polymerizing (A) component may be included, and it should just be adjusted to the compounding quantity of the solvent of the predetermined range finally.

In addition to the solvent, other ingredients include, for example, antioxidants, rust inhibitors, ultraviolet absorbers, conductive materials, electrical insulating materials, antibacterial agents, tackifiers, colorants, fillers, refractive index adjusters. Etc.
Moreover, when mix | blending another additive, although it is based also on the kind, Usually, it is preferable to set it as the value of 0.001 weight part or more and 30 weight part or less with respect to 100 weight part of (A) component.
The reason for this is that when the amount of such other additives is less than 0.001 part by weight, the additive effect may not be exhibited.
On the other hand, when the blending amount of the other additive exceeds 30 parts by weight, it may be difficult to control the base material adhesion and reworkability of the pressure-sensitive adhesive composition.
Accordingly, the lower limit of the amount of other additives is more preferably 0.05 parts by weight or more, and more preferably 2 parts by weight or more with respect to 100 parts by weight of component (A). preferable.
Moreover, it is more preferable to set it as the value of 20 weight part or less with respect to 100 weight part of (A) component about the upper limit of the compounding quantity of another additive, and it is more preferable to set it as a value of 10 weight part or less.

[Second Embodiment]
In the second embodiment, at least (A) an acrylate polymer, (B) a photocurable polyfunctional monomer, (C) a macromonomer, and (D) photopolymerization as a compounding component on a substrate. A pressure-sensitive adhesive sheet comprising an initiator, and a pressure-sensitive adhesive layer made of a cured product of a pressure-sensitive adhesive composition containing (E) a thermal crosslinking agent, and (B) with respect to 100 parts by weight of component (B) ) Component blending amount is 0.1 to 50 parts by weight, component (C) blending component is 0.1 to 20 parts by weight, component (D) blending component is 0.01 to 10 parts by weight, and (E) The pressure-sensitive adhesive sheet is characterized in that the compounding amount of the components is set to a value in the range of 0.01 to 20 parts by weight.
Hereinafter, the adhesive sheet according to the second embodiment of the present invention will be specifically described.

1. Pressure-sensitive adhesive composition and pressure-sensitive adhesive layer (1) Blending composition The blending composition of the pressure-sensitive adhesive composition used for the pressure-sensitive adhesive sheet of the second embodiment can be the same as described in the first embodiment. Therefore, the description here is omitted.

(2) Form Moreover, although it does not restrict | limit especially also about the form of the adhesive layer which consists of an adhesive composition, It is preferable to set it as the adhesive layer which has predetermined thickness.
That is, usually, by forming an adhesive layer having a thickness of 10 μm or more and 200 μm or less, good adhesion and durability to an adherend can be exhibited.
Moreover, the dotted | punctate adhesive layer arrange | positioned regularly or irregularly may be sufficient. That is, by using a point-like pressure-sensitive adhesive layer having an equivalent circle diameter of 1 μm or more and 200 μm or less, the adhesion to the adherend can be finely controlled or good removability can be exhibited.

2. Type of base material (1) The types constituting the base material (base film) include polyacetyl cellulose resin, polyester resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer Coalescence, polystyrene resin, polycarbonate resin, polyethylene resin, polypropylene resin, polymethylpentene resin, cellophane resin, polyacrylic resin, polyurethane resin, epoxy resin, polysulfone resin, polyetheretherketone resin, polyethersulfone resin, polyetherimide resin , Polyimide resin, fluororesin, polyamide resin, norbornene resin, cycloolefin resin, paper, fiber, non-woven fabric, glass fiber and the like alone or in combination of two or more.
And it is also preferable that surface treatments such as corona treatment, primer treatment, saponification treatment, flame oxidation treatment, etc. are applied to the surface of the substrate made of various resins.
This is because such surface treatment can remarkably improve the adhesiveness of the pressure-sensitive adhesive layer to the substrate.
On the other hand, it is also preferable that the base material is provided on both surfaces of the pressure-sensitive adhesive layer, and one of them is composed of a peeling member.
That is, by including such a peeling member, it can be easily applied to an adherend such as a liquid crystal cell.

(2) Form Moreover, although it does not restrict | limit especially as a form of a base material, A sheet form (a film form is included), a nonwoven fabric form, a perforated film, a surface uneven | corrugated film, etc. are mentioned.
For example, a polarizing plate, a retardation plate, a light diffusing polarizing plate, an antireflection film, and the like can be configured by using various sheet-like optical films as the substrate.
Furthermore, by using a substrate having a predetermined colored layer, decorative layer, printing layer, antistatic layer, hard coat layer, etc., an adhesive tape, an adhesive decorative sheet, a marking film, an antistatic film with an adhesive layer, surface protection A film or the like is also preferable.

3. Manufacturing method (1) Preparation process of adhesive composition The preparation process of an adhesive composition is a process of creating the adhesive composition which has a predetermined | prescribed compounding composition.
Therefore, for example, a predetermined acrylic ester monomer, a solvent such as ethyl acetate, and a polymerization initiator such as azobisisobutyronitrile (AIBN) are accommodated in a polymerization vessel equipped with a stirrer and purged with nitrogen. Then, an acrylic ester polymer (ethyl acetate solution, solid content: about 10 to 30% by weight) as the component (A) can be obtained by solution polymerization.
Next, the acrylic ester polymer as the component (A) thus obtained was placed in a container equipped with a stirrer, and then stirred with the stirrer while photocurable polyfunctional as the component (B). A monomer, a macromonomer as the component (C), a photopolymerization initiator as the component (D), a thermal crosslinking agent as the component (E), and an antistatic agent (AS agent) as the component (F) And a silane coupling agent as the component (G) are sequentially added.
Then, normally, it can be set as the adhesive composition which has a uniform compounding composition by stirring and mixing continuously for 10 minutes-24 hours in the state hold | maintained at 20-60 degreeC temperature conditions.

(2) Coating process of pressure-sensitive adhesive composition Next, the coating process of the pressure-sensitive adhesive composition is a known coating method such as a roll coating method, a knife coating method, a gravure coating method, a screen coating method, an ink jet method, or a die coating. In this step, the obtained pressure-sensitive adhesive composition is applied onto a substrate by at least one of the methods and the like, and dried to form a pressure-sensitive adhesive layer.
Therefore, after applying the pressure-sensitive adhesive composition on a substrate such as a polyester film or a polyolefin film by a conventional coating method, for example, by heating and drying at a temperature of 40 to 120 ° C. for 10 seconds to 10 minutes. It can be set as a thick adhesive layer.

After heat drying, the pressure-sensitive adhesive is photocured by irradiating the adhesive composition with a predetermined amount of active energy rays such as ultraviolet rays and electron beams using an ultraviolet irradiation device or an electron beam irradiation device. It can be a layer.
Therefore, for example, when ultraviolet rays are used as the active energy rays, it is preferable to use photocuring conditions with an illuminance of 50 to 1000 mW / cm ² and an exposure amount of 50 to 1000 mJ / cm ² .
Furthermore, when using an electron beam as an active energy ray, it is preferable to set it as photocuring conditions that an irradiation amount becomes the range of 10-1000krad.

In addition, as a modification of the coating process of the pressure-sensitive adhesive composition, after the pressure-sensitive adhesive composition is applied on the release-treated surface of the release film, it is heated and dried, and then bonded to an optical film such as a polarizing plate. It is also possible to produce a photocured pressure-sensitive adhesive layer by irradiating active energy rays through a release film.
That is, in a state where the pressure-sensitive adhesive composition is in an uncured state, it is bonded to an optical film, and then irradiated with a predetermined amount of active energy rays such as ultraviolet rays and electron beams, and more specifically, a seasoning step which is an optional step described later Through this, it is also possible to make a structure of optical film / adhesive layer / release film.

(3) Seasoning Step Next, the seasoning step is an optional step, but is a step in which a pressure-sensitive adhesive composition having a pressure-sensitive adhesive layer on the substrate is promoted to form a pressure-sensitive adhesive layer with improved cohesive strength.
More specifically, this is a step of reliably forming a crosslinked structure by reacting the reactive group of the acrylate polymer as the component (A) with the thermal crosslinking agent as the component (E).
Therefore, it is preferable to carry out such a seasoning step, for example, to stand for 1 day or more and 10 days or less under conditions of room temperature (23 ° C.) and 50% RH to sufficiently crosslink the pressure-sensitive adhesive composition.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1]
1. Preparation of pressure-sensitive adhesive composition (1) (A) Preparation of acrylic acid ester polymer Under a nitrogen atmosphere, in a container equipped with a reflux device and a stirrer, 90 parts by weight of n-butyl acrylate (BA) as a monomer component , 2-phenoxyethyl acrylate (PhEA) 6 parts by weight, acrylic acid (AA) 2.5 parts by weight, and 2-hydroxyethyl acrylate (HEA) 1.5 parts by weight, respectively, and then a polymerization initiator As a component (A), a polymer solution of an acrylate ester copolymer having a weight average molecular weight of 1,500,000 is added. Obtained.
In addition, the weight average molecular weight of (A) acrylic acid ester polymer was measured as a standard polystyrene conversion value using GPC (gel permeation chromatography) method.

(2) Preparation of pressure-sensitive adhesive composition Next, in a container equipped with a stirrer, the obtained polymer solution as component (A) and tolylene diisocyanate modified trimethylolpropane (TDI-tmp) as component (E) , Manufactured by Soken Chemical Co., Ltd., solid content: 75% by weight, ethyl acetate solution), in terms of solid content, the mixture is stirred so that the ratio is 0.1 parts by weight with respect to 100 parts by weight of component (A). While blended.
Next, 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 100% by weight) as component (G) is converted to solid content in terms of 100 parts by weight of component (A). It mix | blended, stirring so that it might become a ratio of 0.2 weight part.

Next, the isocyanuric acid ethylene oxide-modified triacrylate as the component (B) in the container with the stirring device is in a ratio of 10 parts by weight with respect to 100 parts by weight of the component (A) in terms of solid content. Were mixed with stirring.
Next, in a container equipped with the same stirring device, the macromonomer AB-6 (manufactured by Toa Gosei Co., Ltd., one-end methacryloyl group, number average molecular weight: 6000, Tg: -55 ° C) as a component is converted into a solid content. Then, it was blended with stirring so that the ratio was 5 parts by weight with respect to 100 parts by weight of component (A).
Next, Irgacure 500 (trade name, manufactured by Ciba Specialty Chemicals, Inc., benzophenone: 1-hydroxycyclohexyl phenyl ketone mixture (weight) as a photopolymerization initiator as component (D) in a container equipped with the same stirring device The ratio 50:50)) was blended with stirring so that the ratio was 0.7 parts by weight with respect to 100 parts by weight of component (A) in terms of solid content.
Finally, ethyl acetate was diluted and blended so that the solid content concentration was 20% by weight to obtain a pressure-sensitive adhesive composition solution of Example 1.

2. Application of pressure-sensitive adhesive composition solution Next, the obtained pressure-sensitive adhesive composition solution was applied to the release-treated surface of a release film made of polyethylene terephthalate having a thickness of 38 μm as a release film (manufactured by Lintec Corporation, SP-PET3811). It applied using the knife type coating machine so that the thickness after drying might be set to 20 micrometers, and the coating layer was formed.
Next, the coating layer was subjected to heat drying treatment at 90 ° C. for 1 minute to obtain a pressure-sensitive adhesive sheet before the curing treatment.

3. UV irradiation Irradiation of 100 μm thick PET film and 100 μm thick unsaponified TAC polarizing plate (triacetyl cellulose resin polarizing plate) to the coated layer of the obtained adhesive sheet before curing treatment In addition, a laminate 1 for measurement of substrate adhesion and the like and a laminate 2 for durability test were obtained.
Next, each of the obtained laminates 1 and 2 was irradiated with ultraviolet rays from the release film side using an electrodeless lamp (using H bubble) manufactured by Fusion, under the conditions of an illuminance of 200 mW / cm ² and an exposure amount of 200 mJ / cm ^2. Was applied, and the pressure-sensitive adhesive composition was cured with ultraviolet rays.

4). Seasoning of the pressure-sensitive adhesive composition Next, the laminate 1 and the laminate 2 having the pressure-sensitive adhesive composition formed by ultraviolet curing are left to stand (seasoning) under the conditions of 23 ° C. and 50% RH for 7 days. The hydroxy group of the acrylate polymer and the thermal crosslinking agent (tolylene diisocyanate-modified trimethylolpropane) as the component (E) were sufficiently reacted.

5. Evaluation of Adhesive Composition (1) Adhesion Evaluation After peeling off the release film of the obtained laminate 1, the TAC (triacetyl cellulose) film and PMMA (polymethyl), which are base materials, are applied to the adhesive layer. Each film was bonded to a (methacrylate) film. In addition, the surface was unsaponified in all cases, and generally a substrate having poor adhesion was used.
Next, the obtained laminate 1 was cut into a size of 25 mm wide × 100 mm long using a cutting device PN1-600 (manufactured by Hadano Seisakusho Co., Ltd., Super Cutter), and the temperature was 23 ° C. and 50% RH. The sample was left to stand for 1 day under environmental conditions to obtain a measurement sample.
Next, using a tensile tester (Orientec Co., Ltd., Tensilon), the adhesion of the measurement sample was measured under the measurement conditions of peeling rate: 300 mm / min and peeling angle: 180 °. The obtained results are shown in Table 2.

(2) Durability Evaluation Durability as a laminate 2 attached to a polarizing plate under predetermined conditions was evaluated.
That is, the obtained laminate 2 was cut into a size of 233 mm width × 309 mm length using a cutting device PN1-600 (manufactured by Hadano Seisakusho Co., Ltd., super cutter).
Next, after peeling off the release film, the laminate 2 was attached to non-alkali glass 1737 (manufactured by Corning) to obtain a measurement sample.
Subsequently, using an autoclave (manufactured by Kurihara Seisakusho), the measurement sample was pressurized under the conditions of 0.5 MPa, 50 ° C., and 20 minutes.
Next, the measurement samples were put in an oven at 80 ° C. and an oven at 60 ° C. and 90% RH, respectively, and left for 200 hours.
Finally, the measurement sample was taken out from each oven, the appearance was observed using a 10-fold magnifier, and durability was evaluated according to the following criteria. The obtained results are shown in Table 2.
(Double-circle): A bubble, a float, and peeling are not observed in an outer peripheral edge part.
○: No bubbles, floating, or peeling are observed in a portion of 0.6 mm or more from the outer peripheral edge.
(Triangle | delta): In a part 1 mm or more from an outer peripheral edge part, neither a bubble, a float, nor peeling is observed.
X: Bubbles, floating, or peeling are observed in a portion 1 mm or more from the outer peripheral edge.

(3) Haze The haze value of the pressure-sensitive adhesive layer in the obtained laminate 1 was evaluated. That is, the release film of the obtained laminate 1 is peeled off to make a measurement sample, and an integrating sphere type light transmittance measuring device (Nippon Denshoku Industries Co., Ltd., NDH-2000) is used to JIS K 7136: 2000. While conforming, the diffuse transmittance (Td%) and the total light transmittance (Tt%) were measured, and the haze value (%) was calculated by the following formula (1). The obtained results are shown in Table 2.
Haze value (%) = (Td / Tt) × 100 (1)

[Examples 2 to 5]
In Examples 2 to 5, the laminated body 1 for adhesion measurement and the laminated body 2 for durability test were used in the same manner as in Example 1 except that the composition of the pressure-sensitive adhesive composition shown in Table 1 was used. Created and evaluated each. The obtained results are shown in Table 2.
That is, in Example 2, it evaluated by changing the compounding quantity of the macromonomer of (C) component from 5 weight part of Example 1 to 10 weight part.
Moreover, in Example 3, it changed by changing the compounding quantity of (B) component from 10 weight part of Example 1 to 15 weight part.
In Example 4, the amount of component (B) was changed from 10 parts by weight of Example 1 to 15 parts by weight, and the amount of component (C) macromonomer was changed to 5% by weight of Example 1. From the part, it changed to 10 weight part and evaluated.
Furthermore, in Example 5, the type of component (B) was changed to dipentaerythritol hexaacrylate, and the amount of the macromonomer of component (C) was changed from 5 parts by weight to 10 parts by weight for evaluation. .

[Comparative Examples 1-4]
In Comparative Examples 1 to 4, the laminate 1 for adhesion measurement and the laminate 2 for durability test were used in the same manner as in Example 1 except that the composition of the pressure-sensitive adhesive composition shown in Table 1 was used. Created and evaluated each. The obtained results are shown in Table 2.
That is, in Comparative Example 1, the blending amounts of the component (B) and the component (C) were changed from 10 parts by weight and 5 parts by weight of Example 1 to 0 parts by weight, respectively.
Moreover, in the comparative example 2, it evaluated by changing the compounding quantity of (C) component from 5 weight part of Example 1 to 0 weight part.
In Comparative Example 3, the amount of component (B) was changed from 10 parts by weight of Example 1 to 15 parts by weight, and the amount of component (C) was changed from 5 parts by weight of Example 1. Evaluation was performed by changing to 0 parts by weight.
In Comparative Example 4, the type of component (B) was changed to dipentaerythritol hexaacrylate, and the amount of the macromonomer of component (C) was changed from 5 parts by weight to 0 parts by weight for evaluation.

（Ａ）アクリル酸エステル重合体
（Ｂ）光硬化性多官能モノマー
（Ｃ）マクロモノマー
（Ｄ）光重合開始剤
（Ｅ）熱架橋剤
（Ｆ）帯電防止剤
（Ｇ）カップリング剤

(A) Acrylic ester polymer (B) Photocurable polyfunctional monomer (C) Macromonomer (D) Photopolymerization initiator (E) Thermal crosslinking agent (F) Antistatic agent (G) Coupling agent

[Examples 6 to 10]
In Examples 6-10, 1-butyl-3-methylpyridinium hexafluorophosphate, which is an antistatic agent, was used as the component (F) for the pressure-sensitive adhesive compositions of Examples 1-5 shown in Table 1. The laminate 1 for adhesion measurement and the laminate 2 for durability test were prepared in the same manner as in Example 1 except that it was blended at a ratio of 3.2 parts by weight with respect to 100 parts by weight of the component A. Created and evaluated each.
As a result, in Examples 6 to 10, as shown in Table 3, the measurement on adhesion, durability, and haze substantially the same as Examples 1 to 5 except that the predetermined antistatic effect was exhibited. Results were obtained.

As described above, according to the present invention, at least (A) an acrylic polymer, (B) a photocurable polyfunctional monomer, (C) a macromonomer, (D) a photopolymerization initiator, and (E) thermal crosslinking. By making a pressure-sensitive adhesive composition containing a predetermined amount of the adhesive, the compatibility between (A) the acrylic polymer and (B) the photocurable polyfunctional monomer becomes good, and the pressure-sensitive adhesive In the case of a cured product (photocured product) as a layer, good transparency can be stably obtained while maintaining predetermined adhesion and durability.
Accordingly, the pressure-sensitive adhesive composition of the present invention is an optical film (polarizing plate, retardation plate, light diffusing plate, etc.) applied to a liquid crystal display device, a plasma display device, an organic electroluminescence device, an inorganic electroluminescence device, etc. It is expected to make a significant contribution to improving the quality of various films, including the first one.

Claims (8)

As a blending component, at least (A) an acrylate polymer, (B) a photocurable polyfunctional monomer, (C) a macromonomer, (D) a photopolymerization initiator, (E) a thermal crosslinking agent, An adhesive composition comprising
With respect to 100 parts by weight of the component (A), the blending amount of the component (B) is 0.1 to 50 parts by weight, the blending amount of the component (C) is 0.1 to 20 parts by weight, and (D) A pressure-sensitive adhesive composition, wherein the compounding amount of the component is 0.01 to 10 parts by weight, and the compounding amount of the component (E) is a value within the range of 0.01 to 20 parts by weight.   The pressure-sensitive adhesive composition according to claim 1, wherein a haze as a cured product, measured in accordance with JIS K 7136: 2000, is set to a value of 1% or less. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the component (A) is a (meth) acrylic acid ester polymer derived from at least the following components (a1) to (a2) as a monomer component. object.
(A1) (meth) acrylic acid alkyl ester monomer having 1 to 20 carbon atoms in the alkyl group: monomer components other than 100 parts by weight (a2) and (a1), and having a hydroxy group in the molecule Double bond-containing monomer: 0.5 to 10 parts by weight   The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the component (B) is a bifunctional to pentafunctional (meth) acrylate monomer having an average molecular weight of less than 1000. .   The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the component (C) is an acrylate macromonomer having a terminal reactive (meth) acryloyl group.   The component (E) is at least one of an isocyanate compound, an epoxy compound, a carbodiimide compound, an amine compound, a metal chelate compound, and an aziridine compound. The pressure-sensitive adhesive composition according to claim 1.   The component (F) contains an antistatic agent, and the blending amount of the antistatic agent is 0.01 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the component (A). The pressure-sensitive adhesive composition according to any one of claims 1 to 6. On the substrate, at least (A) an acrylate polymer, (B) a photocurable polyfunctional monomer, (C) a macromonomer, (D) a photopolymerization initiator, (E) A pressure-sensitive adhesive sheet comprising a cured product of a pressure-sensitive adhesive composition containing a thermal crosslinking agent,
With respect to 100 parts by weight of the component (A), the blending amount of the component (B) is 0.1 to 50 parts by weight, the blending amount of the component (C) is 0.1 to 20 parts by weight, and (D) The pressure-sensitive adhesive sheet is characterized in that the blending amount of the components is 0.01 to 10 parts by weight, and the blending amount of the component (E) is a value within the range of 0.01 to 20 parts by weight.