KR20200083206A - Adhesive composition, curing product and surface protective film - Google Patents

Abstract

The present invention provides a means of enabling the formation of an adhesive layer which achieves high levels of adhesion and reworkability by having the adhesive strength upon being peeled lower than the adhesive strength in an attached state. In addition to high levels of adhesion and reworkability, the present invention provides a means of improving the punchability and substrate contamination of the adhesive layer, reducing the peeling electrostatic voltage of the adhesive layer, and improving wettability of the adhesive layer to a workpiece. To this end, the present invention provides an adhesive composition characterized by comprising: a urethane prepolymer containing two or more hydroxy groups as component (A); a multifunctional (meth)acrylate as component (B); a crosslinker as component (C); crosslinking particles as component (D); a photo-radical initiator as component (E); and an antistatic agent as component (F), wherein the content of component (D) with respect to 100 parts by weight of component (A) is 0.01-10 parts by mass.

Description

Adhesive composition, cured product and surface protection film {ADHESIVE COMPOSITION, CURING PRODUCT AND SURFACE PROTECTIVE FILM}

The present invention relates to an adhesive composition, a cured product and a surface protection film.

A surface protection film having an adhesive layer is usually used for the purpose of surface protection on surfaces of various displays such as word processors, computers, mobile phones, televisions, various optical components such as polarizing plates or laminates thereof, or various substrates such as electromagnetic plates. Are joined.

As the pressure-sensitive adhesive layer, it is desired to have good adhesion in a bonded state. Adhesion is a property that has sufficient adhesion to an adherend and does not cause defects such as peeling or lifting. In addition, the surface protection film is peeled from the adherend within the manufacturing process or during use, but when the adhesive force is excessive, destruction of cracks or ruptures of the adherend occurs during peeling or adhesive residue is generated on the adherend. There are cases. Therefore, as an adhesive layer, it is calculated|required that it has favorable rework property (removability) at the time of peeling. The rework property refers to a property in which there is no adhesive residue on the adherend or destruction of the adherend and can be easily peeled off.

A urethane-based pressure-sensitive adhesive composition has been studied as a pressure-sensitive adhesive composition from the viewpoint of achieving both such adhesiveness and reworkability.

Patent Literature 1 and Patent Literature 2 disclose that a pressure-sensitive adhesive layer formed of an adhesive composition containing a hydroxyl group-containing polyurethane, an ionic compound, or a trifunctional isocyanate compound can achieve both the adhesive force and rework property of the adhesive film. have.

Patent Document 3 discloses that reworkability can be improved by an adhesive layer formed of an adhesive composition containing a urethane urea resin having a hydroxyl group at the terminal, an ionic compound, and a polyfunctional isocyanate.

[Advanced technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2007-169377

[Patent Document 2] Japanese Patent Publication No. 2005-154492

[Patent Document 3] Japanese Patent Publication No. 2007-238766

The pressure-sensitive adhesive layer formed of the urethane-based adhesive composition (adhesive composition) of Patent Documents 1 to 3 has been tested for compatibility of adhesiveness and reworkability by controlling adhesiveness. However, in this method, adhesiveness and reworkability are both trade-off depending on the adhesive force of the adhesive layer. In other words, when trying to obtain sufficient rework property, the tackiness is insufficient, and when trying to obtain sufficient tackiness, the lack of reworkability becomes a problem. Further, in the urethane-based adhesive composition, there may be a problem that the punching processability and the substrate contamination are insufficient, or that the peeling versus voltage increases. And, depending on the type of urethane-based compound contained in the urethane-based adhesive composition, the wettability of the pressure-sensitive adhesive layer to the adherend may be insufficient. At this time, when joining with the adherend, air enters forcibly, resulting in a problem of poor bonding.

Here, an object of this invention is to provide the means which enables formation of the adhesive layer which was compatible with adhesiveness and rework property to a high level by reducing the adhesive force at the time of peeling than the adhesive force in an adhesive state. In addition, the present invention can improve the punching processability and substrate contamination of the pressure-sensitive adhesive layer in addition to the cohesiveness and rework property, while lowering the peeling vs. voltage of the pressure-sensitive adhesive layer, and at the same time can realize high wettability and high transparency to the adherend of the pressure-sensitive adhesive layer. It aims to provide a means of being.

The said subject of this invention is solved by the following means.

(A) component: urethane prepolymer having two or more hydroxyl groups,

(B) component: polyfunctional (meth)acrylate,

(C) Ingredient: crosslinking agent,

(D) component: crosslinked particles,

(E) component: photo-radical initiator, and

(F) Ingredient: Antistatic agent,

Containing,

The content of the component (D) relative to 100 parts by mass of the component (A) is 0.01 parts by mass or more and 10 parts by mass or less.

According to the present invention, there is provided a means that enables formation of an adhesive layer having both adhesiveness and reworkability at a high level by reducing the adhesive force at the time of peeling than that of the adhesive state.

In addition, according to the present invention, in addition to the cohesiveness and reworkability, it improves the punchability and substrate contamination of the pressure-sensitive adhesive layer, lowers the peeling vs. voltage of the pressure-sensitive adhesive layer, and at the same time provides high wettability and high transparency to the adherend of the pressure-sensitive adhesive layer. Means for realization are provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing explaining the measuring method of the wettability with respect to the to-be-adhered body of the adhesive layer in an Example.

Hereinafter, preferred embodiments of the present invention will be described. In addition, unless otherwise specified, operation, physical properties, etc. are measured under conditions of room temperature (20°C or more and 25°C or less)/relative humidity of 40% RV to 50% RV.

In addition, in this specification, "(meth)acrylate" is a general term for acrylate and methacrylate. Compounds containing (meth), such as (meth)acrylic acid, are likewise generic terms for compounds having "meth" in the name and compounds not having "meth".

In addition, in this specification, "(co)polymer" is a generic term for homopolymers and copolymers.

<Adhesive composition>

One aspect of the present invention

(A) component: urethane prepolymer having two or more hydroxyl groups,

(B) component: polyfunctional (meth)acrylate,

(C) Ingredient: crosslinking agent,

(D) component: crosslinked particles,

(E) component: photo-radical initiator, and

(F) Ingredient: Antistatic agent

Containing,

The content of the component (D) relative to 100 parts by mass of the component (A) relates to an adhesive composition characterized in that it is 0.01 parts by mass or more and 10 parts by mass or less.

The present inventors estimate the mechanism by which the problem is solved by the above configuration as follows.

The urethane-based pressure-sensitive adhesive composition generally forms a pressure-sensitive adhesive layer by curing the urethane-based compound included in the composition with a crosslinking agent such as an isocyanate compound by polymerization or crosslinking reaction. In the conventional urethane-based pressure-sensitive adhesive compositions such as Patent Documents 1 to 3, it has been tested to control the adhesiveness and reworkability by controlling the type of urethane-based compound or crosslinking agent, their content ratio, or reaction conditions. However, while having a trade-off relationship between tackiness and reworkability depending on the tackiness of the pressure-sensitive adhesive layer, there was a problem that it is difficult to achieve both tackiness and reworkability at a high level.

On the other hand, the pressure-sensitive adhesive composition according to one embodiment of the present invention contains (A) component: a urethane prepolymer having two or more hydroxyl groups and (C) component: a crosslinking agent. In addition, the pressure-sensitive adhesive composition according to one embodiment of the present invention further contains (B) component: polyfunctional (meth)acrylate and (E) component: photo-radical initiator. For this reason, light irradiation is performed at the time of rework, (B) component: photopolymerization and crosslinking reaction of the polyfunctional (meth)acrylate or the (meth)acrylic (co)polymer derived therefrom, and the adhesive strength of the pressure-sensitive adhesive It falls significantly. As a result, the pressure-sensitive adhesive layer composed of a cured product of the pressure-sensitive adhesive composition according to one embodiment of the present invention has good adhesion and excellent rework property before light irradiation. Thus, the pressure-sensitive adhesive composition according to one embodiment of the present invention overcomes the technical problem that the adhesiveness and reworkability in the conventional urethane-based pressure-sensitive adhesive composition are in a trade-off relationship. In other words, the pressure-sensitive adhesive composition according to one embodiment of the present invention is capable of separately controlling the pressure-sensitive adhesive force and the adhesive force during rework by a completely different design idea from the conventional urethane-based pressure-sensitive adhesive composition.

Moreover, the adhesive composition which concerns on one aspect of this invention contains (D)component: crosslinked particle|grains. Here, the component (D) forms irregularities on the surface of the pressure-sensitive adhesive layer. And, the unevenness is formed in the pressure-sensitive adhesive layer, the adhesive strength is reduced. Thereby, the adhesive force before light irradiation of the adhesive layer becomes an appropriate range, and adhesiveness improves. Moreover, the adhesive force of the pressure-sensitive adhesive layer at the time of rework decreases, and the rework property of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same is improved.

Moreover, in the pressure-sensitive adhesive composition according to one embodiment of the present invention, the content of the component (D) is in a predetermined range. In other words, the content of the component (D) should be sufficient to obtain the above effect and should not be excessive at the same time. Therefore, compatibility of adhesiveness and rework property is achieved, suppressing the fall of the wettability and transparency of the adhesive layer by the component (D) to the adherend. In addition, since the addition amount of the component (D) is not excessive, it is difficult for the component (D) to drop out, and good punchability can be obtained. In addition, there is no deterioration in the bleed out of the component (F), and low peel-to-voltage is achieved while maintaining good substrate contamination.

On the other hand, the above mechanism is based on speculation, and the correctness and inaccuracy do not affect the technical scope of the present invention.

It is preferable that the pressure-sensitive adhesive composition according to one embodiment of the present invention is thermoset to form an pressure-sensitive adhesive layer. In other words, the pressure-sensitive adhesive composition according to one embodiment of the present invention is preferably a thermosetting pressure-sensitive adhesive composition. In addition, the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition according to one embodiment of the present invention is composed of a cured product of the pressure-sensitive adhesive composition according to one embodiment of the present invention, preferably a thermoset. On the other hand, in the present specification, the thermosetting product is a cured product formed by progressing a crosslinking reaction by heat. The thermosetting does not necessarily require heating, and it is assumed that the cured product cured at room temperature (20°C or more and 25°C or less) is also included.

In addition, a preferred embodiment of the present invention relates to an adhesive composition in which the adhesive strength of the adhesive composition decreases by light irradiation. Here, "the adhesive strength of the pressure-sensitive adhesive composition decreases by light irradiation" means that the pressure-sensitive adhesive strength of the pressure-sensitive adhesive composition itself and its cured product decreases by light irradiation. For this reason, the pressure-sensitive adhesive composition exhibits remarkable excellent rework property by performing light irradiation treatment during rework while reaching a pole in a state of adhesion and showing good adhesion.

Here, the ratio of the adhesive strength after light irradiation to the adhesive strength before the light irradiation treatment of the cured product of the pressure-sensitive adhesive composition or the adhesive strength before and after the light irradiation is preferably in the same range as the pressure-sensitive adhesive layer or adhesive film described later.

Hereinafter, each component constituting the pressure-sensitive adhesive composition according to one embodiment of the present invention will be described in detail.

[(A) component: Urethane prepolymer having two or more hydroxyl groups]

The pressure-sensitive adhesive composition according to one embodiment of the present invention contains component (A): a urethane prepolymer having two or more hydroxyl groups. The component (A) has a function of imparting tack to the pressure-sensitive adhesive layer composed of a cured product of the pressure-sensitive adhesive composition. Such (A) component can contribute to the formation of an adhesive layer by polymerization (preferably thermal polymerization) and crosslinking.

(A) The component is more specifically, while the position of the hydroxyl group in the molecule of the component (A) is not particularly limited, but it is preferable to have hydroxyl groups at least at both terminals. The component (A) is not particularly limited as long as it is a urethane prepolymer that satisfies these, and known materials can be used.

It is well known that urethane prepolymers can be obtained by reacting a polyfunctional isocyanate component with a component having two or more hydroxyl groups (for example, a polyol component). Here, as (A) component, the substance etc. which can be obtained by making (a1) component: polyol and (a2) component: polyfunctional isocyanate react, for example are mentioned.

(a1) It does not specifically limit as a component, A well-known polyol can be used. For example, known polyether polyols, known polyester polyols, known polycarbonate polyols, known polybutadiene polyols, known polyisoprene polyols, and the like can be used. These may be used alone or in combination of two or more. When two or more kinds are used, two or more kinds of substances of the same series may be combined, and one or more kinds of substances of different series may be combined, respectively. Further, the number of hydroxyl groups of these polyols is not particularly limited, but is preferably 2 or more and 4 or less in one molecule.

Examples of the polyether polyol include polyether polyols having a repeating structure such as an alkylene oxide chain such as a methylene oxide chain, an ethylene oxide chain, a propylene oxide chain, and a butylene oxide chain. The alkylene oxide chains may be used alone or in combination of two or more. Among these, it is preferable to have a hydroxyl group bonded to a primary carbon atom from the viewpoint of good reactivity with an isocyanate group. Specific examples include, but are not limited to, polyethylene glycol, polypropylene glycol, polypropylene glycol with terminal polyethylene glycol capping, polytetramethylene glycol, and the like.

As a polyester polyol, what consists of well-known acid component and well-known alcohol component is mentioned. Examples of the acid component include adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid and the like. Moreover, as an alcohol component, for example, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5 -Pentanediol, neopentyl glycol, butylethylpropanediol, glycerin, trimethylolpropane, pentaerythritol, and the like. The acid component and the alcohol component may be used alone or in combination of two or more kinds. In addition, examples of the polyester polyol include substances obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone.

Examples of the polycarbonate polyol include substances obtained by reacting a known carbonate ester or phosgene with a compound having two or more known hydroxyl groups. Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, and diphenyl carbonate. Moreover, as a compound which has two or more hydroxyl groups, an aliphatic polyol, a fatty cyclic polyol, an aromatic polyol, etc. are mentioned, for example. Examples of the aliphatic polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, and tri Propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol , 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1,8-octanediol, etc. are mentioned. Examples of the fatty cyclic polyols include 1,2-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanedimethanol, cycloheptanediol, cyclooctanediol, and hydroxypropylcyclohexanol. . As an aromatic polyol, bisphenol A, bisphenol F, 4,4'-biphenol etc. are mentioned, for example. The carbonate ester and the compound having two or more hydroxyl groups may be used alone or in combination of two or more.

Although the number average molecular weight of (a1) component is not specifically limited, It is preferable that it is 700 or more and 5,000 or less. Moreover, it is more preferable that the number average molecular weight of (a1) component is 1,000 or more and 4,000 or less. Within this range, reaction control during synthesis becomes easier. On the other hand, the number average molecular weight of the component (a1) can be determined by a polystyrene conversion value by gel permeation chromatography (FCC).

Further, if necessary, a part of the component (a1) may be replaced with low molecular polyols or polyvalent amines. Examples of low molecular polyols include ethylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, and butylethylpropanediol. , Glycerin, trimethylolpropane, pentaerythritol, dimer diol, castor oil polyol, and the like. Examples of the polyvalent amines include ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine.

(a2) It does not specifically limit as a component, A well-known polyfunctional isocyanate can be used. For example, aromatic diisocyanates, such as xylylene diisocyanate, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, etc. are mentioned. In addition, for example, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'- dicyclohexylmethane diisocyanate, diisocyanate methyl cyclohexane, tetramethyl xylylene diisocyanate, etc. Aliphatic or aliphatic cyclic diisocyanate etc. are mentioned. In addition, adducts, burettes, isocyanurates, etc. of these diisocyanates may be mentioned. The polyfunctional isocyanate compounds may be used alone or in combination of two or more. Among these, an aliphatic or alicyclic diisocyanate is preferable from the viewpoint that discoloration can be suppressed, and an aliphatic diisocyanate is more preferable from the viewpoint of easier control of the reaction during synthesis.

It is preferable that (A) component contains the urethane prepolymer which has a polyether skeleton and two or more hydroxyl groups. The polyether skeleton has a function of imparting high wettability to various adherends such as glass from its molecular structure. Therefore, when the urethane polymer is used, the wettability of the pressure-sensitive adhesive layer to the adherend is further improved when compared to the case where other urethane prepolymers are used.

The urethane prepolymer having a polyether skeleton and two or more hydroxyl groups is more specifically a urethane oligomer or polyurethane having two or more hydroxyl groups in one molecule having a polyether structure as part of the main chain. The polyether structure means a repeating structure of an alkylene oxide chain such as a methylene oxide chain, an ethylene oxide chain, a propylene oxide chain, and a butylene oxide chain.

Among urethane prepolymers having a polyether skeleton and two or more hydroxyl groups, urethane prepolymers having a polyether skeleton and two or more hydroxyl groups and (meth)acryloyloxy groups are more preferred. According to the urethane prepolymer, reworkability of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same is further improved. It is presumed that the photopolymerization and crosslinking reaction between the component (A) or the component (A) and the component (i) described later or the (co)polymer proceeds according to the component (E) described later. The position of the (meth)acryloyloxy group in the urethane prepolymer molecule is not particularly limited, but it is preferable to have a (meth)acryloyloxy group as the side chain. According to the urethane prepolymer, the effect of improving the rework property of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same becomes higher.

The urethane prepolymer having a polyether skeleton and two or more hydroxyl groups is not particularly limited, and known materials can be used. For example, a substance obtained by reacting the polyether polyol (a2), which is a kind of the (a1) component, with the (a2) component can be given.

Further, the urethane prepolymer having a polyether skeleton and two or more hydroxyl groups and a (meth)acryloyloxy group is not particularly limited, and a known material can be used. For example, (a1) component, (a2) component, (a3) component: what can be obtained by reacting a (meth)acrylate compound having a hydroxyl group or an isocyanate group (a compound having a (meth)acryloyloxy group) have. Here, (a3) component is used for the purpose of introduce|transducing (meth)acryloyloxy group in (A) component.

(a3) The component is not particularly limited, and a (meth)acrylate compound having a known hydroxyl group or isocyanate group can be used. Among these, a (meth)acrylate compound having a hydroxyl group is preferred from the viewpoint of ease of raw material availability, curability and adhesive properties.

Examples of the (meth)acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 3-hydroxy Butyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, hydroxyethylacrylamide, trimethylolpropane di(meth)acrylate, pentaerythritol tri( Meth)acrylate, dipentaerythritol penta (meth)acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, and the like.

Examples of the (meth)acrylate compound having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-bis (( And meta)acryloyloxymethyl)ethyl isocyanate.

In addition, as the urethane prepolymer having a polyether skeleton and two or more hydroxyl groups and (meth)acryloyloxy groups, the following materials may be used in addition. For example, what can be obtained by reacting the reaction product of the (a1) component, a polyfunctional isocyanate having three or more functionalities, and a (meth)acrylate compound having a hydroxyl group is obtained by reacting a compound having two or more isocyanate groups. Here, the polyfunctional isocyanate having a trifunctional or higher functionality is not particularly limited, and for example, the same one as the compound represented by the item (C) described later can be used. In addition, the (meth)acrylate compound having a hydroxyl group is not particularly limited and, for example, the same as the above-mentioned (a3) component can be used. Moreover, what can be obtained by making the reaction product of the (meth)acrylate compound which has the said (a2) component, a triol or more polyol, and an isocyanate group reacts, for example is mentioned. Here, the polyol having a trifunctional or higher functionality is not particularly limited, and, for example, the same compound as the compound represented by the item (a1) can be used. Moreover, the (meth)acrylate compound which has an isocyanate group is not specifically limited, For example, the thing similar to the said (a3) component can be used.

Although the number average molecular weight of (A) component is not specifically limited, It is preferable that it is 1,000 or more. Moreover, it is more preferable that the number average molecular weight of (A) component is 20,000 or more and 500,000 or less, and it is still more preferable that it is 50,000 or more and 200,000 or less. In the above range, the viscosity of the pressure-sensitive adhesive composition becomes a more suitable range, and workability is further improved.

(A) The number average molecular weight of a component can be computed, for example with the following method. A sample is obtained by adding 10 mg of component (A) and 10 ml of TV to the sample bottle, dissolving by standing still overnight, and filtering with a PTV cartridge filter (0.5 μm). As a detector, a RI detector RI8020 (manufactured by Tosoh Corporation), and a series of 2 x TSL-MRR-BRL (manufactured by Tosoh Corporation) x LCC-8020 HPC (manufactured by Tosoh Corporation) are used as the measurement column. The measurement conditions were measured under the conditions of a column temperature of 40°C, a flow rate of 1.0 ml/myn, and a solvent TV, and the number average molecular weight was analyzed by a third-order trend line calibration curve using standard polystyrene manufactured by Tosoh Corporation.

The hydroxyl value of the component (A) is not particularly limited, but is preferably 1 mg·ＫOＫ/Ｈ or more and 230 mg·ＫOＫ/ｇ or less. Further, the hydroxyl value of the component (A) is more preferably 3 mg·ＫOＫ/ｇ or more and 150 mg·ＫOＫ/ｇ or less, and more preferably 4 mg·ＫOＫ/ｇ or more and 100 mg·ＫOＨ/ｇ or less. In the above range, the adhesive force of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same becomes a more appropriate range, and the effect of reducing the occurrence of dropping of the pressure-sensitive adhesive layer is further improved. It is assumed that this is because the polymerization of the component (A) and the component (C) described later and the progress of the crosslinking reaction become more appropriate. On the other hand, the hydroxyl value can be obtained by measurement based on JIS K0070:1992. Here, the hydroxyl group value of the component (A) can be an index of the hydroxyl group content.

(A) The double bond equivalent of the component (polymer mass (g) of 1 m of double bond) is not particularly limited, but is preferably 30,000 g/m or less. Moreover, it is more preferable that the double bond equivalent of (A) component is 20,000 g/m or less, and it is still more preferable that it is 10,000 g/m or less. Moreover, although the double bond equivalent of (A) component is not specifically limited, It is preferable that it is 1,000 g/m or more. In the above range, the adhesive force of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same becomes a more appropriate range, and the occurrence of dropping of the pressure-sensitive adhesive layer is further reduced. It is presumed that the progress of the photopolymerization and crosslinking reaction between the component (A) or the component (A) and the component (B) or the (co)polymer by the component (E) described later becomes more appropriate. Here, when the component (A) has a (meth)acryloyloxy group, the double bond equivalent of the component (A) may be an index of the content of the (meth)acryloyloxy group.

The component (A) may be a synthetic material or a commercial material.

The method for producing the component (A) is not particularly limited, and a known method for synthesizing a urethane compound can be used. Among these, it is preferable to use a known urethanization reaction and apply conditions under which the hydroxyl group becomes excessive. (A) As a component and its manufacturing method, you may use well-known compounds and well-known manufacturing methods described in Unexamined-Japanese-Patent No. 2005-169377, Unexamined-Japanese-Patent No. 2007-168377, etc. Moreover, when manufacturing component (A), you may use a well-known polymerization inhibitor, a well-known urethanization catalyst, etc. as needed.

As commercially available materials, for example, CYABINE (registered trademark) SＨ101 manufactured by Tong Yang Ink Co., Ltd., and Art Resin (registered trademark) 네가N5500, ＵN5500P manufactured by Negami Industries Co., Ltd. can be used. have.

The urethane prepolymer constituting the component (A) may be used alone or in combination of two or more.

[(B) component: polyfunctional (meth)acrylate]

The pressure-sensitive adhesive composition according to one embodiment of the present invention includes (B) component: polyfunctional (meth)acrylate (B). Since the component (B) has a function of photopolymerizing by light irradiation and performing a crosslinking reaction, it can contribute to improvement of rework property by a decrease in adhesive force after light irradiation. (B) When it does not contain a component, adhesive force does not fall by light irradiation, and rework property becomes insufficient.

In one embodiment, the component (B) may include a non-urethane-based polyfunctional (meth)acrylate that does not contain a urethane group.

(B) A component is not specifically limited if it is a compound containing two or more (meth)acryloyloxy groups in one molecule. Among these, a (meth)acrylate or the like, which is bifunctional or more and 10-functional or less, is mentioned as a preferable example. Moreover, (B) component may be 11 functional or more (meth)acrylates, such as 11 or more functional polypentaerythritol poly(meth)acrylates.

As the bifunctional (meth)acrylate, for example, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6 -Hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate , Hydroxypibaric acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, polyethylene glycol di(meth) Acrylate, modified bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene oxide modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanu Late di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, tripentaerythritol di(meth)acrylate, tetrapentaerythritol di(meth)acrylate And the like.

As trifunctional (meth)acrylate, for example, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, tripentaerythritol tri(meth)acrylate, tetrapentaerythritol tri(metha) )Acrylate, propionic acid modified dipentaerythritol tri (meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropaneethoxy tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylic Rate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, polyether tri(meth)acrylate, glycerin propoxy tri(meth)acrylate, tris(acryloyloxyethyl)isocyanurate, and the like. have.

As a tetrafunctional (meth)acrylate, for example, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tetrapentaerythritol tetra(meth) )Acrylate, pentaerythritol ethoxy tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like.

Examples of the pentafunctional (meth)acrylate include dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate, tetrapentaerythritol penta(meth)acrylate, propionic acid-modified dipentaerythritol Penta(meth)acrylate, dipentaerythritol monohydroxy penta

(Meth)acrylate and the like.

As the six-functional (meth)acrylate, for example, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tetrapentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythrate And itol hexa (meth)acrylate.

As a 7-functional (meth)acrylate, tripentaerythritol hepta (meth)acrylate, tetrapentaerythritol hepta (meth)acrylate, etc. are mentioned, for example.

As an 8-functional (meth)acrylate, tripentaerythritol octa (meth)acrylate, tetrapentaerythritol octa (meth)acrylate, etc. are mentioned, for example.

As a 9-functional (meth)acrylate, tetrapentaerythritol nona (meth)acrylate etc. are mentioned, for example.

As a 10-functional (meth)acrylate, tetrapentaerythritol deca (meth)acrylate etc. are mentioned, for example.

Among these, trifunctional (meth)acrylate is preferable, trimethylolpropane tri(meth)acrylate is more preferable, and trimethylolpropane triacrylate is more preferable.

Moreover, you may use urethane (meth)acrylate, polyester (meth)acrylate, etc. as a compound containing 2 or more (meth)acryloyloxy groups in 1 molecule.

The urethane (meth)acrylate is not particularly limited. For example, monomers, oligomers, and the like obtained by reacting a diisocyanate, a polyol, and a (meth)acrylate compound having a hydroxyl group can be given. Moreover, as urethane (meth)acrylate, the urethane (meth)acrylate etc. which were described in Unexamined-Japanese-Patent No. 2002-265650, Japanese Unexamined-Patent No. 2002-355936, Japanese Unexamined-Patent No. 2002-067238 etc. are mentioned, for example. .

As the diisocyanate, for example, TDI, MDI, BDI, IPPD, BMDI, and the like can be mentioned.

Examples of polyols include poly(propylene oxide)diol, poly(tetramethylene oxide)diol, ethoxylated bisphenol A, ethoxylated bisphenol S, spiroglycol, caprolactone modified diol, carbonate diol, and the like.

Examples of the (meth)acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidol di(meth)acrylate, and pentaerythritol triacrylic. Rate etc. are mentioned.

The specific urethane (meth)acrylate is not particularly limited. For example, make an adduct of TDI and hydroxyethyl acrylate, an adduct of IPDI and hydroxyethyl acrylate, an adduct of BDD and pentaerythritol triacrylate (PETA), an adduct of TDI and PETA , A compound obtained by reacting the remaining isocyanate with dodecyloxy hydroxypropyl acrylate, an adduct of 6,6 nylon with TDI, an adduct of pentaerythritol with TDI and hydroxyethyl acrylate, and the like.

The polyester (meth)acrylate is obtained by condensing (meth)acrylic acid on the basis of hydroxyl groups remaining on the polyester backbone synthesized from polyol and dibasic acid to form an acrylate.

The specific polyester acrylate is not particularly limited. For example, reactants of phthalic anhydride/propion oxide/acrylic acid, reactants of adipic acid/1,6-hexanediol/acrylic acid, and reactants of trimellitic acid/diethylene glycol/acrylic acid.

Moreover, it is preferable that (B) component contains a hydroxyl group further. The occurrence of dropping of the pressure-sensitive adhesive layer is further reduced by having the structure. This is because the polymerization and crosslinking reaction between the component (A), the component (B) or the (co)polymer and the component (C) proceeds during the polymerization and crosslinking reaction between the component (A) and the component (C). I guess.

Although the hydroxyl value of (B) component is not specifically limited, It is preferable that it is 100 mg*ＫOＨ/ｇ or less. Further, the hydroxyl value of the component (B) is more preferably 50 mg·ＫOＨ/ｇ or less, and more preferably 30 mg·Ｋ•Ｋ/ｇ or less (lower limit 0 mg·ＫOＫ/g). In the above range, the adhesive force of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same becomes a more appropriate range, and the occurrence of dropping of the pressure-sensitive adhesive layer is further reduced. The polymerization of the component (B) or its (co)polymer and the component (C) and the progress of the crosslinking reaction are within a suitable range, and the polymerization and crosslinking reaction of the component (A) and the component (C) proceeds better. I guess it is because.

On the other hand, the hydroxyl value can be obtained by measurement in accordance with JIS K0070:1992.

The component (B) may be a synthetic material or a commercial material. As commercially available substances, for example, Shin-Nakamura Chemical Industry Co., Ltd., A-TMBT, A-TMM, A-TMM-3L, A-TMM-3LM-N, AMT-35E, A- TMM, A-9550, A-DFP, ARONICS (registered trademark) M-305, M-402, M-405 manufactured by Dong-A Synthetic Corporation, Osaka Organic Chemical Industry Co., Ltd. And VISCOAT (registered trademark) #295, TMPTA, #802, and TRIPEA.

The polyfunctional (meth)acrylate may be used alone or in combination of two or more.

The content of the component (i) in the pressure-sensitive adhesive composition (total amount when two or more types are included) is not particularly limited, but is preferably 1 part by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the component (A).

Moreover, it is more preferable that content of (B) component is 5 mass parts or more and 250 mass parts or less with respect to 100 mass parts of (A) component. The content of the component (B) is more preferably 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the component (A). In the above range, the adhesive force of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same becomes a more appropriate range. It is presumed that the content ratio of the component (A) and the component (B) is in a suitable range, and the adhesive force is in a better range. Moreover, in the said range, rework property of the adhesive layer or the adhesive film which has this improves more. It is assumed that this is because the photopolymerization and crosslinking reaction of the component (i) by light irradiation during rework proceeds more. Further, in the above range, when the component (B) further has a hydroxyl group, the occurrence of dropping of the pressure-sensitive adhesive layer is further reduced. It is assumed that the polymerization and crosslinking reaction between the (A) component and the (B) component or the (co)polymer and (C) component proceeds during the polymerization and crosslinking reaction between the component (A) and the component (C). Doing.

Accordingly, as a preferred example of the component (B), the content of the component (i) relative to 100 parts by mass of the component (A) is 10 parts by mass or more and 150 parts by mass or less, and the hydroxyl value of the component (B) is 100 mg. And less than or equal to ＨOＨ/ｇ.

[(C) component: crosslinking agent]

The pressure-sensitive adhesive composition according to one embodiment of the present invention includes (C) component: a crosslinking agent. The component (C) has a function of advancing polymerization (preferably thermal polymerization) and crosslinking with the component (A). For this reason, the adhesive force of the adhesive composition and the adhesive force after light irradiation can be made into an appropriate range, and it can contribute to the cohesion of adhesiveness and rework property. When (C) component is not contained, adhesive force will become excessive, and rework property will also be insufficient.

In one embodiment, component (C) may be a thermosetting crosslinking agent.

In one embodiment, the component (C) may be a crosslinking agent that does not include a (meth)acrylic group (or (meth)acrylate group).

The component (C) is not particularly limited as long as it can advance polymerization and crosslinking reaction with the component (A). For example, an isocyanate type crosslinking agent, a carbodiimide type crosslinking agent, an oxazoline type crosslinking agent, an epoxy type crosslinking agent and an aziridine type crosslinking agent, peroxide, etc. are mentioned. Here, peroxide means a compound having a peroxide structure "-O-O-" in the molecular structure. These may be used alone or in combination of two or more. When two or more kinds are used, two or more kinds of substances of the same series may be combined, and one or more kinds of substances of different series may be combined, respectively.

The isocyanate-based crosslinking agent is not particularly limited, and a compound (isocyanate compound) having a known isocyanate group can be used. As a compound which has an isocyanate group, monofunctional isocyanate and polyfunctional isocyanate are mentioned. Among these, polyfunctional isocyanates are preferred. Examples of the polyfunctional isocyanate include bifunctional isocyanate (a compound having two isocyanate groups) and trifunctional or higher isocyanate (a compound having three or more isocyanate groups).

As the bifunctional isocyanate, for example, aliphatic diisocyanates, fatty cyclic diisocyanates, aromatic diisocyanates, carbodiimide-modified diisocyanates of these diisocyanates, or these diisocyanates are main chain ends, side chains or side chains The polymer compound etc. which have in a terminal are mentioned.

Examples of the aliphatic diisocyanates include 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (ＨDI), trimethylhexamethylene diisocyanate (TMDDI), lysine diisocyanate, norbornane diisocyanate methyl (NDDI), and the like. Can be lifted.

Examples of the fatty cyclic diisocyanates include transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPPD), H6-BDI (hydrogenated BDDI), and H12-MDDI (hydrogenated MDDI).

Examples of aromatic diisocyanates include dimer acid diisocyanate, 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), and 4,4'-diphenyl Methane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (ＸDI), tetramethyl xyl And relene diisocyanate (TMDDI), toluidine diisocyanate (TODI), and 1,5-naphthalene diisocyanate (NDI).

Examples of the trifunctional or higher isocyanate include an isocyanurate product obtained by polycondensing the bifunctional isocyanate to isocyanurate-modified product, an adduct-modified product obtained by adduct-modifying the bifunctional isocyanate, and the difunctional isocyanate and 3 such as glycerin and trimethylolpropane. And a biuret-modified alcohol-containing burette, a polymer compound having the bifunctional isocyanate or its adduct, burette or isocyanurate at the main chain end, side chain or side chain end.

The carbodiimide-based crosslinking agent is not particularly limited, and a known carbodiimide compound can be used. Examples of the carbodiimide compound include a high molecular weight polycarbodiimide produced by subjecting a diisocyanate to a decarbonation condensation reaction in the presence of a carbodiimide catalyst. Examples of diisocyanates provided for the decarbonation condensation reaction include 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, and 3,3'-dimethyl-4,4. '-Diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene Diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, and the like. Moreover, as a carbodiimide catalyst which can be used for a decarbonation condensation reaction, for example, 1-phenyl-2-phosphorene-1-oxide, 3-methyl-2-phosphorene-1-oxide, 1-ethyl-3 And phosphorene oxides such as -methyl-2-phosphorene-1-oxide, 1-ethyl-2-phosphorene-1-oxide, and 3-phosphorene isomers thereof.

The oxazoline-based crosslinking agent is not particularly limited, and a known oxazoline compound can be used. As an oxazoline compound, an oxazoline group containing polymer is mentioned, for example. Examples of the oxazoline compound include an oxazoline group-containing acrylic polymer and an oxazoline group-containing acrylic/styrene polymer. Here, the oxazoline group-containing acrylic polymer includes, for example, an oxazoline group-containing acrylic polymer containing a main chain made of an acrylic skeleton and having an oxazoline group on the side chain of the main chain. The oxazoline group-containing acrylic/styrene polymer includes, for example, an acrylic skeleton or a main chain made of a styrene skeleton, and has an oxazoline group-containing acrylic/styrene polymer containing a main chain on the side chain of the main chain. And the like. On the other hand, as an oxazoline group, a 2-oxazoline group, 3-oxazoline group, 4-oxazoline group, etc. are mentioned, for example.

The epoxy-based crosslinking agent is not particularly limited, and a known epoxy compound can be used. Examples of the epoxy compound include a liquid epoxy compound and the like. The liquid epoxy compound is preferred in that it facilitates mixing when preparing the pressure-sensitive adhesive composition.

The aziridine-based crosslinking agent is not particularly limited, and a known aziridine compound can be used. Examples of the aziridine compound include a polyfunctional aziridine compound having a plurality of aziridine rings. Examples of the polyfunctional aziridine compound include compounds disclosed in U.S. Patent No. 3,225,013, U.S. Patent No. 4,490,505, U.S. Patent No. 5,534,391, and Japanese Unexamined Patent Publication No. 2003-104970. As a polyfunctional aziridine compound, a trifunctional aziridine compound (a compound having three aziridine rings) can be preferably used. As trifunctional aziridine compounds, for example, trimethylolpropane tris[3-aziridinylpropionate], trimethylolpropane tris[3-(2-methyl-aziridinyl)-propionate], trimethylolpropane tris [2-aziridinyl butyrate], pentaerythritol tris-3-(1-aziridinylpropionate) and pentaerythritol tetrakis-3-(1-aziridinylpropionate). .

The peroxide is not particularly limited, and a known substance can be used. Peroxides are, for example, diisopropyl peroxydicarbonate, bis(2-ethylhexyl)peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate (alias peroxy2 bis(4-t- Butylcyclohexyl), bis(screw-scec-butylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, Bis-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, bis(4-methylbenzoyl)peroxide, dibenzoylperoxide (benzoyl peroxide), t -Butyl peroxybutyrate and the like.

Among these, an isocyanate-based crosslinking agent or peroxide is preferable, and an isocyanate-based crosslinking agent is more preferable. And it is more preferable to use an isocyanate type crosslinking agent alone or to use an isocyanate type crosslinking agent and peroxide together.

Examples of the isocyanate-based crosslinking agent include hexamethylene diisocyanate (ＨDI) or pentamethylene diisocyanate (PDI), their adducts, burettes or isocyanurates, or polymer compounds having them at the main chain end, side chain or side chain ends. This is preferred. Moreover, as an isocyanate type crosslinking agent, the adduct body of hexamethylene diisocyanate (BDI) or pentamethylene diisocyanate (PDI) is more preferable. Or, a polymer compound obtained by condensation reaction of hexamethylene diisocyanate (BDI) or pentamethylene diisocyanate (PDI) with diol is more preferable. Here, as a preferable example of hexamethylene diisocyanate (BDD), 1,6-hexamethylene diisocyanate etc. are mentioned. Moreover, 1,5-pentamethylene diisocyanate etc. are mentioned as a preferable example of pentamethylene diisocyanate (PDI). According to these isocyanate crosslinking agents, the polymerization between the component (A) and the progress of the crosslinking reaction can be progressed more efficiently.

As the peroxide, bis(4-t-butylcyclohexyl) peroxydicarbonate is preferable. According to the peroxide, the polymerization and crosslinking reaction between the component (A) can proceed more efficiently.

The component (C) may be a synthetic material or a commercial material. As a commercially available substance, in an isocyanate-based crosslinking agent, for example, Coronate (registered trademark) L (e.g., L-45E, etc.) manufactured by Tosoh Corporation, ＨL, ＨＸ, 2030, 2031, Mitsui Chemical Co., Ltd. TAKANATE (trademark) D-102, D-110N, D-200, D-202, DURANATE (registered trademark) 24A-100 manufactured by Asahi Chemical Chemical Co., Ltd., TPA -100, TV-100, P301-75E, E402-80B, E402-90T, E405-80T, TSE-100, D-101, D-201, Residential Bayer Urethane's SMIDULE ( Trademark) N-75, N-3200, N-3300, Mitsui Chemicals Corporation STABIO (registered trademark) D-370N, D-376N, Nippon Soda Co., Ltd. And Nisso-TP (registered trademark) TTP1001, etc. are mentioned. In the carbodiimide-based crosslinking agent, for example, CARBODILITE (registered trademark) V-01, V-03, V-05, V-07, V-09 manufactured by Nisshinbo Chemical Co., Ltd. And the like. In the oxazoline-based crosslinking agent, for example, EPOCROS (registered trademark) ＷS-300, ＷS-500, ＷS-700, K-1000 series, K- 2000 series, etc. are mentioned. In the epoxy-based crosslinking agent, for example, Mitsubishi Gas Chemical Co., Ltd.'s TTRAD-C, TREAD-X, ADADA's ADEKA RESIN EP series, EPR series, Daicel's celloxide And series. Examples of the aziridine-based crosslinking agent include CHEMITITE (registered trademark) PF-33 and D-22E manufactured by Nippon Shokubai Co., Ltd. In the peroxide, for example, PAKMILL (registered trademark) ND, PAROIL (registered trademark) manufactured by Ilyu Co., Ltd., IP, NP, IPP, SVP, TVP, OPP, 355, L, SA, per Rota (PEROCTA) ND, O, Perhexyl (PERHEXYL) (registered trademark) ND, PF, O, I, Perbutyl (PERBUTYL) (registered trademark) ND, NTP, Pp, O, L, I, A, PERHEXA (registered trademark) 25O, MCC, TMB, HFC, C, 25Z, 22, Nyper (NYPER) (registered trademark) PMK, HMT, HMS, HMT-K40, HMT-M, Pertetra (PERTETRA) (registered trademark) A and the like.

The amount of the component (C) added in the pressure-sensitive adhesive composition is not particularly limited as long as it is a content capable of advancing polymerization and crosslinking reaction with the component (A).

(C) When the component contains an isocyanate-based crosslinking agent (a compound having an isocyanate group), the equivalent ratio of the total amount of isocyanate groups of the compound having an isocyanate group to the total amount of hydroxyl groups of the component (A) in the pressure-sensitive adhesive composition (NCO (total) (mole)/ Ox (mol) is preferably 0.2 or more and 10 or less. The equivalent ratio is more preferably 0.4 or more and 10 or less, and more preferably 0.5 or more and 6 or less. Moreover, it is especially preferable that the equivalent ratio is 1 or more and 4.5 or less. In the above range, the adhesive force of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same becomes a more appropriate range, and the occurrence of dropping of the pressure-sensitive adhesive layer is further reduced. It is assumed that this is because the progress of polymerization and crosslinking reaction with (A) component becomes more appropriate.

It is preferable that (C) component contains a bifunctional isocyanate or a trifunctional or higher isocyanate.

(C) When the component contains an isocyanate-based crosslinking agent (a compound having an isocyanate group), the equivalent ratio of the isocyanate group content of the bifunctional isocyanate to the total amount of isocyanate groups of the compound having the isocyanate group in the pressure-sensitive adhesive composition (NCO (bifunctional) (molar) It is preferable that /NCO (total) (molar) is 0 or more and 1 or less. Moreover, it is more preferable that the equivalent ratio is more than 0 and 1 or less because it is preferable that the compound which (C) component has an isocyanate group contains bifunctional isocyanate. Further, the equivalent ratio is preferably more than 0 and less than 1, more preferably 0.25 or more and less than 1. The equivalent ratio is particularly preferably 0.5 or more and 0.95 or less, and particularly preferably 0.7 or more and 0.9 or less. In the above range, the adhesive force of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same becomes a more appropriate range. In particular, above the lower limit, occurrence of dropping of the pressure-sensitive adhesive layer is further reduced. It is assumed that this is because the progress of polymerization and crosslinking reaction with (A) component becomes more appropriate. Moreover, the bleed-out of the additive component, such as the (i) component mentioned later, to the adhesive layer can be suppressed more reliably below the said upper limit. It is assumed that this is because the crosslinking density becomes higher and diffusion of these components in the pressure-sensitive adhesive layer becomes more difficult to occur.

It is preferable that (C) component contains a trifunctional or more isocyanate. According to the isocyanate, the bleed-out of an additive component such as the component (i) described later to the pressure-sensitive adhesive layer can be more reliably suppressed, and the substrate contamination is further improved. It is assumed that this is because the crosslinking density between the (A) components in the pressure-sensitive adhesive layer becomes higher, and diffusion of these components in the pressure-sensitive adhesive layer becomes more difficult to occur.

(C) When a component contains a crosslinking agent other than an isocyanate type crosslinking agent, the content of the crosslinking agent (the total amount when two or more types are included) is 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the component (A). desirable. Moreover, it is more preferable that content of the said crosslinking agent is 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts of (A) component. Moreover, it is more preferable that content of the said crosslinking agent is 0.5 mass part or more and 5 mass parts or less with respect to 100 mass parts of (A) component. In the above range, the adhesive force of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same becomes a more appropriate range, and the occurrence of dropping of the pressure-sensitive adhesive layer is further reduced. It is presumed that it is because the progress of polymerization and crosslinking reaction between (A) component or (B) component or its (co)polymer becomes more appropriate.

[(D) component: crosslinked particles]

The pressure-sensitive adhesive composition according to one embodiment of the present invention includes (D) component: crosslinked particles. In the present specification, the crosslinked particles represent particles having a crosslinked structure as at least a part of the structure constituting the particles. The component (D) has a function of forming irregularities on the surface of the pressure-sensitive adhesive layer. Here, the unevenness is formed in the pressure-sensitive adhesive layer, whereby the adhesive force decreases. Therefore, (D) component can contribute to being able to further improve adhesiveness by making the adhesive force before light irradiation of the adhesive layer or the adhesive film which has this into an appropriate range. Moreover, (D) component can further reduce the adhesive force at the time of rework, and can contribute to the improvement of rework property. When (D) component is not contained, the adhesive force of the adhesive force before light irradiation becomes excessive, resulting in poor adhesiveness. Moreover, the adhesive force after light irradiation becomes excessive, and the rework property becomes insufficient. Particularly, the component (D) can cause a decrease in adhesive strength due to light irradiation even when a crosslinking agent (C) having no (meth)acrylic group is used as described above.

(D) A component is not specifically limited, A well-known crosslinked particle can be used. Examples include styrene crosslinked particles, (meth)acrylic crosslinked particles, fluorine-modified (meth)acrylic crosslinked particles, styrene-(meth)acrylic crosslinked particles, urethane crosslinked particles, and silicone crosslinked particles.

The styrene-based crosslinked particles are crosslinked particles comprising at least 50% by mass or more of styrene-based monomers.

The (meth)acrylic crosslinked particles are crosslinked particles having at least 50% by mass or more of a structural unit derived from a monomer having a (meth)acryloyloxy group ((meth)acrylate monomer). Here, examples of the (meth)acrylate monomer include a combination of a known monofunctional (meth)acrylate and a known polyfunctional (meth)acrylate. As a preferable specific example, (meth)acrylic-type crosslinked particle|grains include crosslinked particle|grains which mainly have methyl polymethacrylate (PMMA).

The styrene-(meth)acrylic crosslinked particles are crosslinked particles having at least 50% by mass or more of a structural unit derived from a styrene monomer or a structural unit derived from a (meth)acrylate monomer.

The urethane-based crosslinked particles are crosslinked particles composed of a polymer compound having at least 50% by mass or more of urethane bonds or urea bonds (urea bonds). Here, examples of the polymer compound having a urethane bond or a urea bond include, for example, a reaction product of a known polyfunctional isocyanate and polyol, a reaction product of a known polyisocyanate and water, and the like.

As the silicone-based crosslinked particles, for example, those commonly referred to as silicone rubbers or silicone resins, and crosslinked particles having a solid substance as a main component at room temperature are mentioned. Preferred specific examples include a silicone resin powder in a solid state at room temperature (a polyorganosilsesquioxane cured product having a cross-linked structure in which a siloxane bond has a three-dimensional network) and the like.

Moreover, as crosslinked particle|grains, crosslinked rubber particle|grains other than the substance exemplified above are mentioned other than this, for example.

Among these, (meth)acrylic crosslinked particles or silicone crosslinked particles are preferred from the viewpoints of cohesiveness and reworkability, punchability, wettability and transparency, and silicone crosslinked particles are more preferable.

The component (D) may be a core-shell particle having a cross-linked structure constituting the cross-linked particles as a core portion or a shell portion. Further, the component (D) may be hollow particles.

(D) A component may be the coated particle which further covered the surface of the particle|grains containing the crosslinked structure which comprises the said crosslinked particle|grains with a coating material. The coating material is not particularly limited, and a known coating material that can be used for coating the particles can be used. Examples include natural resins, synthetic resins, silicone resins, metals, and inorganic compounds.

(D) The shape of the component is not particularly limited. For example, a spherical shape, an oval shape, an irregular shape, a needle shape, a plate shape, a hollow shape, a columnar shape, an awl shape, etc. are mentioned. Among these, from the viewpoint of deterioration in adhesive strength, it is preferably spherical or elliptical, and more preferably spherical.

The average particle diameter of the component (D) is not particularly limited, but is preferably 0.5 μm or more and 30 μm or less. Further, the average particle diameter of the component (D) is more preferably 0.5 μm or more and 25 μm or less, and more preferably 0.5 μm or more and 20 μm or less. Above the lower limit, the tackiness of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having it becomes better, and reworkability is further improved. It is assumed that this is because the size of the unevenness formed on the surface of the pressure-sensitive adhesive layer becomes larger, the adhesion force becomes a more appropriate range, and the adhesion force after light irradiation is further reduced. Further, below the upper limit, the wettability of the adhesive layer to the substrate is further improved. It is presumed that this is because the unevenness of the surface of the pressure-sensitive adhesive layer becomes smaller and air is more difficult to force into the adhesive surface.

The color of the component (D) is not particularly limited, but is preferably transparent from the viewpoint of ensuring transparency of the adhesive film.

The component (D) may be a synthetic material or a commercial material. As commercially available materials, for example, ART PEARL (registered trademark) manufactured by Negami Industries Co., Ltd., JR series, SEE series (eg, SEE-010T, SEE-020T, etc.), G series, GS series , J series, MB series, MB series, JR series (above, crosslinked acrylic beads, transparent type), C series, P series, GB series, U series, CE series, AM series, HI series, MB series, MB series, TV series, C-TV series, RTV, RS series, RS series, series series, series series, series series (top, cross-linked urethane beads, transparent type), Shin-Etsu Chemical Co., Ltd. 600, AMP-601, AMP-602, AMP-605, X-52-7030 (above, silicon composite powder), AMP-P-597, AMP-P-598, AMP-P-594, and X-52-875 (above, silicone rubber powder ), BMP-590, BMP-701, X-52-854, X-52-1621 (above, silicone resin powder) and the like.

The method for producing these crosslinked particles is not particularly limited, and a known method can be employed. For example, a method of preparing a crosslinked polymer through polymerization methods such as suspension polymerization, sheet polymerization or emulsion polymerization, and then washing, drying, classifying and the like can be given. In addition, a method of preparing a polymer compound having a reactive functional group and crosslinking the polymer compound may be mentioned.

The crosslinked particles may be used alone or in combination of two or more.

The content of the component (D) in the pressure-sensitive adhesive composition (total amount when two or more types are included) is 0.01 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component (A). Below the lower limit, the adhesive force becomes excessive, resulting in poor adhesiveness. Moreover, the adhesive force of the pressure-sensitive adhesive layer at the time of rework becomes excessive, and the rework property of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same becomes insufficient. Moreover, when it exceeds the said upper limit, adhesive force will become under and adhesiveness will fall. In addition, when the amount of the component (D) added becomes excessive, dropping of the component (D) tends to occur, and the punchability is deteriorated. Moreover, the unevenness of the surface of the pressure-sensitive adhesive layer becomes excessive, the wettability of the pressure-sensitive adhesive layer to the adherend decreases, light diffusion tends to occur, and transparency decreases. Thereby, it is more preferable that the content of the component (D) is 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the component (A), from the viewpoints of adhesiveness, reworkability, punchability, wettability, and transparency. Moreover, it is more preferable that content of (D) component is 0.1 mass part or more and 1 mass part or less with respect to 100 mass parts of (A) component.

[(E) component: Photo radical initiator]

The pressure-sensitive adhesive composition according to one embodiment of the present invention includes (E) component: photo-radical initiator. The component (E) has a function of generating radicals by irradiation with light, and the photopolymerization and crosslinking of the component (B) can proceed, thereby contributing to an improvement in reworkability due to a decrease in adhesion after light irradiation. When (E) component is not contained, adhesive force does not fall by light irradiation, and rework property becomes insufficient.

(E) It does not specifically limit as a component, A well-known substance can be used. Examples include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, anthraquinone compounds, and acylphosphine oxide compounds. In addition, 3,3', 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, acrylated benzophenone, etc. are also mentioned.

Examples of the acetophenone compound include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-(4-isopropylphenyl)-2- Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyphenylketone, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl- And [4-(methylthio)phenyl]-2-morpholino-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, and the like.

Examples of the benzoin compound include benzoin compounds such as benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of benzophenone compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-me And methoxybenzophenone.

As a thioxanthone compound, for example, thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl And thioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone.

Examples of the anthraquinone compound include 4,4'-dimethylaminothioxanthone (alias = minerazketone), 4,4'-diethylaminobenzophenone, α-acyloxime ester, benzyl, methyl benzoylformate, 2-ethyl anthraquinone etc. are mentioned.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, and the like.

Examples of the acrylated benzophenones include 3,3', 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and acrylated benzophenone.

Among these, an acylphosphine oxide compound is preferable, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is more preferable from the viewpoint that the rework property of the pressure-sensitive adhesive layer or the adhesive film having the same can be further improved. Do.

The component (E) may be a synthetic material or a commercial material. Examples of commercially available substances include, for example, OMNIRAD (registered trademark) 184, 369, 651, 819, 907, 1173, TPO H, and DFSS Japan Corporation's ESAcure (ESACURE) (registered trademark) ＫIP150, TTV, Nippon Kayaku Co., Ltd. ＫＡＹＡＣＣＲＥ(registered trademark) ＢＭS, ＤＭＢＩ and the like.

The photo-radical initiators may be used alone or in combination of two or more.

The content of the component (E) in the pressure-sensitive adhesive composition (the total amount when two or more kinds are included) is not particularly limited, but is preferably 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the component (A). Moreover, it is more preferable that content of (E) component is 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts of (A) component, and it is more preferable that it is 0.5 mass part or more and 5 mass parts or less. Moreover, it is especially preferable that content of (E) component is 1 mass part or more and 2 mass parts or less with respect to 100 mass parts of (A) component. Within the above range, the rework property of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same is further improved. It is assumed that this is because the photopolymerization and crosslinking reaction of the component (i) by light irradiation during rework proceeds more.

[(F) component: Antistatic agent]

It is preferable that the adhesive composition which concerns on one aspect of this invention contains (F) component: antistatic agent. The component (F) has a function of improving electrical conductivity and may contribute to a decrease in the surface resistance value of the pressure-sensitive adhesive layer. For this reason, the generation of static electricity can be effectively suppressed, especially when it is necessary to peel (rework) due to bonding errors after bonding to a liquid crystal cell or the like as an adherend. As a result, it is possible to stably prevent dust from easily adhering to the surface of a polarizing plate or the like, confusion in liquid crystal alignment, or electrostatic destruction of peripheral circuit elements. Thereby, when it does not contain (F) component, peeling versus voltage becomes excessive.

(F) A component is not specifically limited, A well-known substance can be used. For example, ionic liquids, such as ionic liquids and bis(fluorosulfonyl)imide salts, ion conducting agents, surfactants, and the like.

Examples of the ionic liquid include phosphonium ions, pyridinium ions, pyrrolidinium ions, imidazolium ions, guanidinium ions, ammonium ions, isouronium ions, thiouronium ions, and piperidinium ions , Cationic components such as pyrazolium ions, sulfonium ions, quaternary ammonium, quaternary phosphonium, halogen ions, nitrate ions, sulfate ions, phosphate ions, perchlorate ions, thiocyanate ions, thiosulfate ions, It may be a substance having an anion component such as sulfite ion, tetrafluoroborate ion, hexafluorophosphate ion, formic acid ion, oxalic acid ion, acetate ion, trifluoro acetate ion, alkylsulfonic acid ion, and the like.

Specific examples of the ionic liquid include 1-allyl-3-methylimidazolium chloride, 1,3-dimethylimidazolium chloride, 1,3-dimethylimidazolium dimethylphosphate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium iodide, 1-ethyl-3-methanesulfonate, 1-ethyl-3-methylimidazolium tetrafluoroborate , 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium-p-toluenesulfonate, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3 -Methylimidazolium chloride, 1-methyl-1-propyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-methylpyrrolidinium bromide, 1-butyl-1- Methylpiperidinium bromide, 1-ethylpyridinium chloride, 1-ethylpyridinium bromide, 1-butylpyridinium chloride, 1-butylpyridinium bromide, 1-butyl-3-methylpyridinium chloride, 1-ethyl-3-methylpyridinium ethylsulfate, 1-butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridinium hexafluorophosphate, trimethylpropylammonium bis(trifluoromethane Sulfonyl)imide, tributylmethylammonium bis(trifluoromethanesulfonyl)imide (alias: tri-n-butylmethylammonium bistrifluoromethanesulfone imide), tetrabutylammonium chloride, tetrabutylammonium bromide And cyclohexyltrimethylammonium bis(trifluoromethanesulfonyl)imide, tetrabutylphosphonium bromide, and the like.

Examples of the surfactant include non-ionic surfactants and ionic surfactants.

Examples of the non-ionic surfactant include polyethylene glycol alkyl ether, polyoxyalkylene alkyl ether, and the like.

Examples of the ionic surfactant include positive ionic surfactants such as alkyltrimethylammonium halide having 8 to 22 carbon atoms, and negative ionic surfactants such as alkyl sulfate.

Among these, ionic liquids are preferable, and tributylmethylammonium bis(trifluoromethanesulfonyl)imide is more preferable.

The component (E) may be a synthetic material or a commercial material. As a commercially available substance, for example, 3M (trademark) ionic liquid type antistatic agent BFC-4400 manufactured by 3M Japan Co., Ltd. is mentioned as ionic liquid.

The antistatic agent may be used alone or in combination of two or more.

The content of the component (F) in the pressure-sensitive adhesive composition (when two or more are included, the total amount thereof) is not particularly limited, but is preferably 0.01 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of the component (A). Moreover, it is more preferable that content of (F) component is 0.1 mass part or more and 20 mass parts or less with respect to 100 mass parts of (A) component, and 0.5 mass part or more and 15 mass parts or less are more preferable. Further, the content of the component (F) is more preferably 2 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the component (A). Above the lower limit, peeling versus voltage of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having it is further reduced. In addition, below the upper limit, the contamination of the substrate of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film having the same is further improved.

[(G) Ingredient: Stabilizer]

The pressure-sensitive adhesive composition according to one embodiment of the present invention may further contain (G) component: stabilizer as long as the effects of the present invention are not impaired. (G) The component stabilizes radicals generated by weak light (for example, ultraviolet rays) of the illumination level, and suppresses the progress of the photocuring reaction of the pressure-sensitive adhesive composition, the cured product, and the pressure-sensitive adhesive layer before light irradiation treatment. Have By this, by adding the component (G), the pressure-sensitive adhesive composition, its cured product, and pressure-sensitive adhesive layer can be stored in an environment where weak light (for example, ultraviolet light) is irradiated, for example, under LED lighting. , Can improve storage. On the other hand, since the irradiation light at the time of irradiation is large, a large amount of radicals are generated at the time of light irradiation, and the stabilizing effect due to the component (G) does not adhere. Thereby, the photocuring reaction at the time of light irradiation proceeds even in the presence of (G) component, and the adhesive strength of the pressure-sensitive adhesive layer can be reduced. In the present specification, the stabilizer is said to represent any of antioxidants, light stabilizers, polymerization inhibitors, or ultraviolet absorbers.

The component (G) is not particularly limited as long as it is an antioxidant, a light stabilizer, a polymerization inhibitor, or an ultraviolet absorber, and known materials can be used. Among these, it is preferable that it is an antioxidant and a light stabilizer.

Examples of the antioxidants include hindered phenolic antioxidants and phosphorus antioxidants.

Although it is not specifically limited as a hindered phenolic antioxidant, For example, the compound etc. which have a steric hindrance hydroxy phenyl group are mentioned. The steric hindrance hydroxy phenyl group is not particularly limited as long as it is a bulky substituted hydroxy phenyl group. For example, a substance having a substituted or unsubstituted alkyl group at positions 2 and 6 of the hydroxy phenyl group may be mentioned, but is not limited thereto. As hindered phenolic antioxidants, triethylglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, thiodiethylene-bis [3-(3,5-Di-t-butyl-4-hydroxyphenyl)propionate, benzenepropionic acid 3,5-bis(1,1-dimethyl)-4-hydroxy-C7 to C9 branched alkyl ester , 4,6-bis(dodecylthiomethyl)-o-cresol, 3,3',3",5,5',5"-hexa-t-butyl-α,α'α"-(mesitylene- 2,4,6-triyl)tri-p-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2 ,4,6(1H,3H,5H)-trione, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-yl Amino)phenol, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], ethylenebis(oxyethylene)bis[3-(5- t-butyl-4-hydroxy-m-tril)propionate], hexamethylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], isooctyl- 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4 -Hydroxybenzyl)benzene, 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4 ,8,10-tetraoxaspiro[5·5]undecane, N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionamide], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), N, N'-bis [3-(3,5-di-t -Butyl-4-hydroxyphenyl)propionyl]hydrazine, diethyl [(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl]phosphate, 3,5-di-t- Butyl-4-hydroxybenzylphosphonate-diethyl ester, 3, 3', 3'', 5, 5', 5"-hexa-t-butyl-a, a', a"-(mesh Styrene-2,4,6-triyl) Tri-p-cresol, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-tris(4-t-butyl-3-hydroxy Hydroxy-2,6-dimethyl)isocyanurate, 1,3,5-tris(4-sec-butyl-3-hydroxy-2,6-dimethyl) isocyanurate, 1,3,5-tris (4-Neopentyl-3-hydroxy-2,6-dimethyl)isocyanurate acid, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidene Bis(4-methyl-6-t-butylphenol), tris-(3,5-di-t-butyl-4-hydroxy benzyl)-isocyanurate, tris-(3,5-di-t- Butyl-4-hydroxybenzyl)-isocyanurate, polycondensate of p-chloromethylstyrene and p-cresol, polycondensate of p-chloromethylstyrene and divinylbenzene, polycondensate of p-cresol and divinylbenzene And isobutylene reactants.

Examples of the phosphorus antioxidant include triphenyl phosphate, tris (2,4-di-t-butylphenyl) phosphate, diphenyl octyl phosphate, diphenyl isodecyl phosphate, phenyl diisodecyl phosphate, and tetrakis (2,4) -Di-t-butylphenyl)-4,4'-biphenylenephosphite, trisnonylphenylphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearylpenta Erythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2, 4-dicumylphenyl)pentaerythritol-diphosphite, tetrakis(2,4-di-t-butylphenyl)(1,1-biphenyl)-4,4'-diylbisphosphonite, di-t -Butyl-m-cresyl-phosphonite, distearylpentaerythritol diphosphite, di(2,4-di-t-butylphenyl)-pentaerythritol diphosphite, di(2,6-di-t -Butyl-4-methylphenyl)-pentaerythritol diphosphite, 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-ditridecyl)phosphite, cyclic neopentane tetrayl bis (Octadecyl)phosphite, diisodecylpentaerythritol diphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, bis(tridecyl)pentaerythritol diphosphite, bis (Nonylphenyl)pentaerythritol diphosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, tetraphenyltetra(tridecyl)pentaerythritoltetraphosphite, tetra(tridecyl)-4,4 '-Isopropylidene diphenyl diphosphite, tetraphenyl dipropylene glycol diphosphite, and the like.

Examples of the light stabilizer include hindered amine light stabilizers (XALS).

Although it does not specifically limit as a hindered amine light stabilizer (XALS), For example, the compound etc. which have a steric hindrance piperidyl group are mentioned. Here, the steric hindrance piperidyl group is not particularly limited as long as it is a bulky, substituted piperidyl group. For example, a substance having one or more or less than two alkyl groups at positions 2 and 6 of the piperidyl group may be mentioned, but is not limited thereto. Examples of the hindered amine-based light stabilizer (XALS) include bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-penta Methyl-4-piperidinyl) sebacate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin)-4-yl] Amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, decanic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidi Neil) ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-butyl-2-(4-hydroxy-3,5-di-t-butylbenzyl)propane Dionate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4 -(Meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4 -(Meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethyl Piperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1- (meta )Acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acrylo Ilamino-2,2,6,6-tetramethylpiperidine, 1-crotonyl-4-crotonyloxy-2,2,6,6-tetramethylpiperidine, etc. are mentioned.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-t-butyl catechol, and 2,6-dibutyl-4-methylphenol.

Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers such as 2,4-dihydroxy-benzophenone and 2-hydroxy-4-methoxy-benzophenone. Further, for example, benzo such as 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, etc. And a triazole-based ultraviolet absorber. Also, for example, 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy And triazine-based ultraviolet absorbers such as -4-ethoxyphenyl)-1,3,5-triazine.

Among these, an antioxidant or a light stabilizer is preferable, and a hindered phenolic antioxidant or a hindered amine light stabilizer (PALS) is more preferable. Then, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], bis(1,2,2,6,6-pentamethyl-4- Piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate are more preferred.

The component (G) may be a synthetic material or a commercial material. As commercially available materials, hindered phenolic antioxidants are, for example, IRSAANO Corporation (registered trademark) 1010, 1010ＦＦ, 1035, 1035ＦＦ (W&C), 1076, 1076ＦD, 1098, 1135, 1330, 1530L, 1726, 245, 245ＦＦ, 259, 3114, 565. In addition, the hindered amine-based light stabilizer (XALS) is, for example, Tian uｖinn (registered trademark) 111 ＦDL, 123, 144, 292, 5100, 123-DＷ, 622 Ｆ, PA 144, 765, 770DE, manufactured by BASF Japan Ltd. VT 55 ＦＢ, 783 ＦLDL, 791 ＦＢ, CVImagssorr (registered trademark) 2020 ＬLDL, 944 ＦDL, 944LD, and the like.

Antioxidants, light stabilizers, polymerization inhibitors or ultraviolet absorbers may be used alone or in combination of two or more. When two or more kinds are used, two or more kinds of substances of the same series may be combined, and one or more kinds of substances of different series may be combined, respectively.

As a commercial product related to the combination of other series, for example, a blend of a UV absorber and a hindered amine-based light stabilizer (BALS) is, for example, BASF Japan Co., Ltd. ティノｕｖｉｎ (registered trademark) 5050, 5060, 5151, 5333-DＷ And the like.

The content (i) of the component (i) in the pressure-sensitive adhesive composition is not particularly limited. However, in order to obtain the effect of the above-mentioned (iii) component better, the content of the (G) component is not contained as more than 5 parts by mass relative to 100 parts by mass of the (A) component, that is, the It is preferable that the content is 5 parts by mass or less. This is because when the content of the component (G) exceeds 5 parts by mass, the amount of radicals stabilized by the component (G) increases, and the progress of the photocuring reaction during light irradiation may be suppressed. Moreover, it is more preferable that content of (G) component is 3 mass parts or less with respect to 100 mass parts of (A) component, and it is still more preferable that it is 0.5 mass parts or less. In the above-mentioned range, the effect of reducing the adhesive force after the light irradiation treatment of the pressure-sensitive adhesive layer is not affected. In addition, the content of the component (G), that is, the content of the component (i) in the thermosetting pressure-sensitive adhesive composition (total amount when two or more types are included) is 100 mass of the component (A) It is preferable that it is more than 0 parts by mass with respect to parts. This is because it is possible to stabilize radicals generated under an environment in which weak light (for example, ultraviolet rays) of the pressure-sensitive adhesive layer is irradiated, for example, under LED lighting. Moreover, it is more preferable that content of (G) component is 0.01 mass part or more with respect to 100 mass parts of (A) component, and it is still more preferable that it is 0.05 mass part or more. In the above range, the storage property is further improved in an environment in which weak light (for example, ultraviolet light) is irradiated, for example, under LED lighting. Thereby, when an adhesive composition contains (G) component, as an example of the preferable range of the content, 0 mass part more than 5 mass parts or less with respect to 100 mass parts of (A) component is mentioned.

[Other ingredients]

The pressure-sensitive adhesive composition according to one embodiment of the present invention may further contain a known additive as long as the effects of the present invention are not impaired. It is not particularly limited as an additive. Examples include curing accelerators, lithium salts, fillers, softeners, anti-aging agents, tackifying resins, leveling agents, antifoaming agents, plasticizers, dyes, pigments, treatment agents, fluorescent brighteners, dispersants, and lubricants.

[Method of manufacturing adhesive composition]

The preparation method (manufacturing method) of the adhesive composition which concerns on one aspect of this invention is not specifically limited, A well-known method can be used. The pressure-sensitive adhesive composition according to one embodiment of the present invention can usually be followed by mixing each component described above. The mixing method is not particularly limited. Examples of the mixing method include a method in which components are collectively mixed, each component is sequentially added and mixed, or a plurality of components are mixed, and then the remaining components are mixed. After mixing, it is preferable to stir to obtain a uniform mixture. If necessary, stirring may be performed in a place where light of a specific wavelength is shielded until uniformity in a stirrer or the like. Moreover, if necessary, you may warm and stir until it becomes uniform with a stirrer or the like. Here, the stirring time is not particularly limited, for example, 10 minutes or more and 5 hours or less. In addition, when heating, the temperature after heating is not particularly limited, and for example, 30°C or more and 40°C or less is mentioned.

Another aspect of the present invention relates to a pressure-sensitive adhesive composition solution containing the pressure-sensitive adhesive composition and a solvent. In the present specification, the solution or dispersion containing the above-described pressure-sensitive adhesive composition and solvent is referred to as "adhesive composition solution". Here, the pressure-sensitive adhesive composition solution may be used to improve the uniformity of the pressure-sensitive adhesive composition by mixing, or may be used as a coating solution for forming the pressure-sensitive adhesive layer described later.

It is preferable to use a solvent (solvent, dispersion medium) when preparing the pressure-sensitive adhesive composition or when preparing a coating liquid. The solvent is not particularly limited, but is preferably an organic solvent. It does not specifically limit as an organic solvent. For example, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, hexane, acetone, cyclohexanone, 3-pentanone, acetonitrile, propionitrile, isobutyronitrile, valeronitrile, dimethyl sulfoxide, dimethyl And formamide. Among these, methyl ethyl ketone or ethyl acetate is preferred. The organic solvents may be used alone or in combination of two or more.

The concentration of the pressure-sensitive adhesive composition in the pressure-sensitive adhesive composition solution is not particularly limited, but is preferably 20% by mass or more and 99% by mass or less with respect to the total mass of the pressure-sensitive adhesive composition solution. The concentration of the pressure-sensitive adhesive composition is more preferably 30% by mass or more and 95% by mass or less with respect to the total mass of the pressure-sensitive adhesive composition solution. In the above range, the dryness of the pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition is further improved, and the coatability when used as a coating liquid is further improved.

On the other hand, preparation of the pressure-sensitive adhesive composition and the pressure-sensitive adhesive composition solution and storage thereof are preferably performed in a light-shielding environment. For example, when the adhesive strength of the pressure-sensitive adhesive composition is lowered by ultraviolet irradiation, it is preferable to prepare and store in an ultraviolet shielding environment, for example, in a yellow room. This is because the progress of the photocuring reaction of the pressure-sensitive adhesive composition can be further suppressed, and the effect of reducing the adhesive strength of the pressure-sensitive adhesive layer after light irradiation can be further improved.

<Adhesive layer and manufacturing method thereof>

Another aspect of the present invention relates to a cured product of the pressure-sensitive adhesive composition. Another aspect of the present invention also relates to a pressure-sensitive adhesive layer composed of a cured product of the pressure-sensitive adhesive composition. Here, as mentioned above, it is preferable that it is a thermosetting adhesive composition as an adhesive composition, and it is preferable that it is a thermosetting thing as a hardened|cured material.

On the other hand, as described above, the thermosetting product is a cured product formed by the progress of a crosslinking reaction by heat. It is assumed that the thermosetting does not necessarily require heating, and also includes a cured product cured at room temperature (20°C or more and 25°C or less).

In the cured product according to one embodiment of the present invention, the adhesive strength decreases by light irradiation. For this reason, the pressure-sensitive adhesive layer according to one embodiment of the present invention exhibits excellent reworkability by performing light irradiation treatment while reaching a pole in a state of adhesion and showing good adhesion. Here, with respect to the adhesive force before light irradiation treatment of the adhesive film which concerns on one aspect of this invention, it is preferable that the ratio of the adhesive force after light irradiation is the same range as the ratio of the adhesive force after light irradiation treatment of the adhesive film mentioned later.

It is preferable that the adhesive force of the adhesive layer which concerns on one aspect of this invention is the same range as the adhesive force of the adhesive film mentioned later from a viewpoint of coexistence of adhesiveness and rework property. On the other hand, the adhesive force can be measured using a tensile tester, and details of the measurement method are described in Examples.

Moreover, it is preferable that the adhesive force after the light irradiation process of the adhesive layer which concerns on one aspect of this invention is the same range as the adhesive force after the light irradiation process of the adhesive film mentioned later from a viewpoint of rework property. On the other hand, the adhesive force after the light irradiation treatment can be measured using a tensile tester, and details of the measurement method are described in Examples. The preferable irradiation light and the preferable range of the irradiation energy in the light irradiation treatment of the pressure-sensitive adhesive layer are all the same as the preferable conditions for the light irradiation treatment of the pressure-sensitive adhesive film described later.

The method of forming the pressure-sensitive adhesive layer is not particularly limited, and a known method can be used. It is preferable that it is a method of coating the pressure-sensitive adhesive composition itself or the pressure-sensitive adhesive composition solution on a support, and subjecting the formed coating film to heat drying treatment or heat treatment as necessary.

In addition, the coating thickness (thickness after drying, thickness of the pressure-sensitive adhesive layer) of the pressure-sensitive adhesive composition is not particularly limited. The thickness may be selected depending on the purpose of the pressure-sensitive adhesive layer or the type of the base material when used as an adhesive film. The thickness is preferably 1 μm or more and 500 μm or less. Further, the thickness is more preferably 10 μm or more and 300 μm or less, and further preferably 20 μm or more and 200 μm or less.

The coating method is not particularly limited, and a known method can be used. For example, natural coater, knife belt coater, floating knife, knife overroll, knife on offset, spray, dip, kiss roll, squeeze roll, reverse roll, air blade, curtain flow coater, doctor blade, wire bar, die coater, And a method using a device such as a comma coater, a baker applicator, and a gravure coater.

When the pressure-sensitive adhesive composition itself is used to form the pressure-sensitive adhesive layer, the heat treatment temperature of the pressure-sensitive adhesive composition is not particularly limited. If it is a thermosetting adhesive composition, it will not be specifically limited if it is a temperature at which the progress of the crosslinking reaction can be sufficient. The heat treatment temperature is preferably 20°C or higher and 150°C or lower, and more preferably 40°C or higher and 150°C or lower. Further, the heat treatment temperature is also preferably 50°C or more and 140°C or less, and particularly preferably 80°C or more and 130°C or less. In addition, in this case, the heat treatment time of the pressure-sensitive adhesive composition is not particularly limited. The heat-curable pressure-sensitive adhesive composition is not particularly limited as long as the time during which the crosslinking reaction can proceed sufficiently. The heat treatment time is preferably 5 seconds or more and 20 minutes or less, more preferably 30 seconds or more and 10 minutes or less, and even more preferably 1 minute or more and 7 minutes or less. By making heating conditions into the said range, the crosslinking reaction of an adhesive composition can advance more suitably, and the adhesive layer which has a better adhesive force can be obtained.

In addition, when using the pressure-sensitive adhesive composition solution for the formation of the pressure-sensitive adhesive layer, the heat-drying treatment temperature of the pressure-sensitive adhesive composition solution is not particularly limited. If it is a thermosetting adhesive composition, it will not be specifically limited if it is a temperature at which the progress of the crosslinking reaction can be sufficiently performed. The heat drying treatment temperature is preferably 40°C or more and 150°C or less, more preferably 50°C or more and 140°C or less, and even more preferably 80°C or more and 130°C or less. Further, in this case, the heat drying treatment time is not particularly limited. The heat-curable pressure-sensitive adhesive composition is not particularly limited as long as the time during which the crosslinking reaction can proceed sufficiently. The heating and drying treatment time is preferably 5 seconds or more and 20 minutes or less, more preferably 30 seconds or more and 10 minutes or less, and even more preferably 1 minute or more and 7 minutes or less. The solvent can be sufficiently removed by setting the heat drying treatment conditions to the above range. Moreover, if it is a thermosetting adhesive composition, the crosslinking reaction of an adhesive composition can progress more suitably, and the adhesive layer which has a better adhesive force can be obtained.

In addition, when forming the pressure-sensitive adhesive layer, it is preferable to further perform an aging treatment after application and heat treatment or heat drying treatment. By performing the aging treatment, the crosslinking reaction of the pressure-sensitive adhesive composition can proceed more appropriately to obtain a pressure-sensitive adhesive layer having better adhesion. The aging treatment conditions are not particularly limited, and known conditions in the method for producing the pressure-sensitive adhesive layer can be used. The aging treatment temperature is preferably 10°C or higher and 40°C or lower, and more preferably room temperature (20°C or higher and 25°C or lower). The aging treatment humidity is preferably a relative humidity of 10% RＨ or more and 80% R or less, and preferably 40% RＨ or more and 50% RＨ or less. The aging treatment time is preferably 1 day or more and 7 days or less. Thereby, as an example of preferable aging treatment conditions, it is exemplified to perform the aging treatment for 7 days in an environment of 23°C 50% RV. By setting the aging treatment conditions in the above range, the crosslinking reaction of the pressure-sensitive adhesive composition can be more appropriately performed to obtain a pressure-sensitive adhesive layer having better adhesion.

On the other hand, the aging treatment is preferably performed in a state in which the support, the coating film after heat drying and heating, and the release film described later are laminated in this order.

On the other hand, it is preferable to form and store the pressure-sensitive adhesive layer in a light-shielding environment. For example, when the adhesive strength of the pressure-sensitive adhesive composition and its cured product is lowered by ultraviolet irradiation, it is preferable to form and store in an ultraviolet shielding environment, for example, in a yellow room. This is because the progress of the photocuring reaction of the pressure-sensitive adhesive composition and its cured product can be further suppressed, and the effect of reducing the adhesive strength of the pressure-sensitive adhesive layer after light irradiation can be further improved.

<Adhesive film>

Another aspect of the present invention relates to a pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer (that is, the pressure-sensitive adhesive layer) composed of a substrate and a cured product of the pressure-sensitive adhesive composition. In other words, the form can also be referred to as an adhesive film comprising a pressure-sensitive adhesive layer composed of a substrate and a cured product of the pressure-sensitive adhesive composition. Here, as mentioned above, it is preferable that it is a thermosetting adhesive composition as an adhesive composition, and it is preferable that it is a thermosetting thing as a hardened|cured material. In addition, the details of the adhesive layer are as described above.

It is preferable that the adhesive film is a surface protection film. The surface protection film is a film that is bonded to the surface of members such as various optical components and various substrates for the purpose of surface protection until the production process of the product or the final product is used.

The pressure-sensitive adhesive layer is disposed on at least one surface of the substrate directly or with another member interposed therebetween. Among these, the pressure-sensitive adhesive layer is preferably disposed directly on one surface of the substrate or with another member interposed therebetween.

The substrate is not particularly limited, and known materials can be used. Among these, it is preferable that it is a resin film. This is because the resin film is excellent in properties required for adhesive film applications, particularly surface protection film applications, such as high surface protection, good handling, and high transparency. The resin constituting the resin film is not particularly limited, and a known material can be used. Here, "a film called a resin as a main component" indicates that the content of the resin to be noted relative to the total mass of the resin film is 50% by mass or more. Here, the content of the resin to be noted is preferably 70% by mass or more, and more preferably 80% by mass or more, with respect to the total mass of the resin film. Moreover, it is preferable that content of the resin of interest is 90 mass% or more with respect to the total mass of a resin film, and it is especially preferable that it is 95 mass% or more (upper limit 100 mass %).

As the resin constituting the resin film, for example, a film containing a resin such as a polyester resin, a cellulose resin, a polycarbonate resin, an acrylic resin, a styrene resin, an olefin resin, or a polyamide resin as a main component is used. Can be lifted. Examples of the polyester resins include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate. Examples of the cellulose-based resin include diacetyl cellulose and triacetyl cellulose. As an acrylic resin, polymethyl (meth)acrylate etc. are mentioned, for example.

Examples of the styrene resin include polystyrene and acrylonitrile-styrene copolymer. Examples of the olefin-based resin include polyethylene, polypropylene, polyolefins having a cyclic structure (preferably a norbornene structure), and ethylene-propylene copolymers. As polyamide resin, nylon 6, nylon 6,6, aromatic polyamide etc. are mentioned, for example. Among these, it is preferable that it is a film which has a polyester resin as a main component (a polyester resin film). Moreover, it is more preferable that it is a film which has a polyethylene terephthalate as a main component (polyethylene terephthalate film, PET film). The resin material constituting the resin film may be used alone or in combination of two or more.

The thickness of the substrate is not particularly limited, but is preferably 10 μm or more and 500 μm or less. Further, the film thickness of the substrate is more preferably 20 μm or more and 200 μm or less, and further preferably 40 μm or more and 100 μm or less.

The substrate may be subjected to surface treatment. The surface treatment is not particularly limited, and a known method can be used.

The adhesive film may further have other members in addition to the base material and the adhesive layer. It does not specifically limit as another member, The various members which a well-known adhesive layer has are mentioned. For example, an intermediate layer provided between the base material and the pressure-sensitive adhesive layer or a release film bonded to a surface opposite to the base side of the pressure-sensitive adhesive layer can be given. Among these, a release film is preferred. Meanwhile, the intermediate layer or the release film is not particularly limited, and a known material that can be used in the adhesive film field can be used.

As a release film, the product etc. which treated the surface of a polyethylene terephthalate film with a silicone release agent, for example are mentioned. As a commercial product of a release film, Mitsubishi Resin Corporation's DIA FOIL (trademark) MR#38 etc. are mentioned, for example.

The manufacturing method of the adhesive film which concerns on one aspect of this invention is not specifically limited, A well-known method can be used. It is preferable that the above-mentioned pressure-sensitive adhesive composition itself or the above-mentioned pressure-sensitive adhesive composition solution is coated on a substrate, and a method of performing heat drying treatment or heat treatment as necessary on the formed coating film.

One preferred example of the pressure-sensitive adhesive film according to one embodiment of the present invention by this is a surface protective film having a pressure-sensitive adhesive layer composed of a cured product of the pressure-sensitive adhesive composition, disposed on one side of the resin film and the resin film.

On the other hand, it is preferable to manufacture and store the adhesive film in a light-shielding environment. For example, when the adhesive strength of the pressure-sensitive adhesive composition and its cured product is decreased by ultraviolet irradiation, it is preferable to manufacture and store in an ultraviolet shielding environment, for example, in a yellow room. This is because the progress of the photocuring reaction of the pressure-sensitive adhesive composition and its cured product can be further suppressed, and the effect of reducing the adhesive strength of the pressure-sensitive adhesive layer after light irradiation can be further improved.

In addition, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film according to one embodiment of the present invention is lowered by light irradiation treatment. For this reason, the pressure-sensitive adhesive film according to one embodiment of the present invention exhibits remarkable excellent reworkability by performing light irradiation treatment during rework while reaching a pole in a state of adhesion and showing good adhesion. The ratio of the adhesive strength after the light irradiation treatment to the adhesive strength before the light irradiation treatment of the adhesive film according to one embodiment of the present invention is not particularly limited. The ratio is preferably smaller from the viewpoint of rework property. When the adherend is made of glass, it is preferable that the corresponding ratio of the adhesive film according to one embodiment of the present invention, particularly the surface protection film, is 0% or more and 75% or less. Further, the ratio is more preferably 0% or more and 55% or less, and more preferably 0% or more and 35% or less. Moreover, it is more preferable that the ratio is 0% or more and 30% or less. And, it is particularly preferable that the ratio is 0% or more and 20% or less.

The adhesive force before the light irradiation treatment of the adhesive film according to one embodiment of the present invention is not particularly limited. When the adherend is made of glass, it is preferable that the corresponding adhesive strength of the pressure-sensitive adhesive film according to one embodiment of the present invention, especially the surface protection film, is 5 g/25 mm or more and 20 g/25 mm or less. The adhesive force is more preferably 6 g/25 mm or more and 15 g/25 mm or less, and more preferably 8 g/25 mm or more and 14 g/25 mm or less. In the above range, the adhesive film and the rework property are compatible with a higher level. On the other hand, the adhesive force can be measured using a tensile tester, and details of the measurement method are described in Examples.

The adhesive force after the light irradiation treatment of the adhesive film which concerns on one aspect of this invention is not specifically limited if it is a value smaller than before the light irradiation treatment. This adhesive force is preferable, so that the value is small from a viewpoint of rework property. When the adherend is made of glass, the adhesive force of the adhesive film according to one embodiment of the present invention, particularly the surface protection film, is not particularly limited as long as it is lower than the adhesive force before light irradiation of the adhesive film, but is preferably less than 5 g/25 mm. Do. Further, the adhesive force is more preferably 3 g/25 mm or less, and more preferably 2.5 g/25 mm or less (lower limit 0 g/25 mm). On the other hand, the adhesive force after the light irradiation treatment can be measured using a tensile tester, and details of the measurement method are described in Examples.

In the adhesive film of the present invention, the ratio of the peel strength of the following formula 1 in relation to substrate contamination may be 70% or more, preferably 70% to 100%. Within this range, there may be an effect that does not contaminate the substrate of the protective film:

[Equation 1]

Ratio of peel strength = PS2/PS1 x 100

(In the above formula 1, PS1 is the peel strength when peeling the pressure-sensitive adhesive sheet from the alkali-free glass in the direction of 180° at a peel rate of 23° C. × 50% RＨ, 300 mm/min (unit: g/25 mm),

PS2 is laminated with the pressure-sensitive adhesive film of the present invention on an alkali-free glass, and after standing at 40° C. for 2 weeks, the pressure-sensitive adhesive film is peeled from the alkali-free glass in a direction of 180° at a peeling rate of 2400 mm/min, and then the After laminating the pressure-sensitive adhesive sheet on the side from which the pressure-sensitive adhesive film was peeled off, the pressure-sensitive adhesive strength when peeling the pressure-sensitive adhesive sheet in the direction of 180° at a peeling rate of 23° C. × 50% RＨ, 300 mm/min (unit: g/25 mm)).

The adhesive sheet may be used in the following examples, but is not limited thereto.

The adhesive film of the present invention may have a wettability of less than 5 seconds. In the above range, the lamination time for the adherend is short, so that fairness can be improved. The wettability can be measured by the following method: an adhesive sheet is prepared by adhering a PET film to the upper surface of the adhesive film, and the prepared adhesive sheet is 25 mm wide and 200 mm long, and is cut into a rectangular shape with a top surface. Prepared, the test piece is laminated so that only the length of 5mm width 25mm of the lower surface of the adhesive film adheres to the surface of the alkali-free glass, and the angle between the alkali-free glass surface and the adhesive film is 20° to 30°. After temporarily fixing, when the specimen is bonded to the alkali-free glass surface by gravity alone, the time at which the adhesive film wets and spreads on the alkali-free glass surface is measured. 1 is a schematic diagram for evaluating wettability. For details about FIG. 1, refer to the wettability evaluation section below.

The irradiation light in the light irradiation treatment is not particularly limited as long as the photopolymerization and crosslinking of the component (i) by the (E) component can proceed. The irradiation light may be appropriately selected depending on the type of the (E) component and (B) component. Among these, ultraviolet rays are preferable from the viewpoints of controllability, handling properties, and cost, and more preferably ultraviolet rays having a wavelength of 200 nm or more and 400 nm or less.

The light irradiation device is not particularly limited, and a known device can be used. In the case of ultraviolet irradiation treatment, for example, light sources such as metal halide lamps, high pressure mercury lamps, ＵＶ-LED lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and light lasers can be exemplified. .

The amount of light irradiation energy is not particularly limited. In the case of ultraviolet ray irradiation treatment, ultraviolet light irradiation energy amount is preferably 50mJ / cm ² or more 5000mJ / cm ² or less. In this case, the ultraviolet irradiation amount of energy is more preferably, and preferably, 300mJ / cm ² or more 1500mJ / cm ² or less more preferably 100mJ / cm ² or more 3000mJ / cm ² or less.

In the adhesive film according to one embodiment of the present invention, it is preferable that the adhesive strength before UV irradiation after the LED stability test (adhesive strength after the LED stability test) does not change from the adhesive strength before UV irradiation when manufactured and stored under an ultraviolet shielding environment. . Here, the LED stability test is performed by leaving the adhesive film manufactured and stored in an ultraviolet shielding environment for 15 days (360 hours) in a test environment under 23° C. x 50% RＨ and LED lighting (500L uｘ). The value of the adhesive force after the LED stability test divided by the value of the adhesive force before ultraviolet irradiation when manufactured and stored in an ultraviolet shielding environment is referred to as an adhesive force ratio. When the adherend is made of glass, the adhesive strength ratio (glass adhesive strength ratio) of the adhesive film, especially the surface protection film, which affects one embodiment of the present invention is not particularly limited, but is preferably 0.8 or more and 1.2 or less.

In the adhesive film according to one embodiment of the present invention, the adhesive strength after UV irradiation after the LED stability test (the adhesive strength after the UV treatment after the LED stability test) is produced and stored in an ultraviolet shielding environment, and then subjected to UV irradiation treatment It is preferable not to change from the adhesive force after ultraviolet irradiation. Here, the LED stability test is performed by leaving the adhesive film manufactured and stored under an ultraviolet shielding environment for 15 days (360 hours) under a test environment under 23°C x 50% RV and LED lighting (500L uｘ). A value obtained by dividing the value of the adhesive force after the UV treatment after the LED stability test by manufacturing and storing it in an ultraviolet shielding environment and the value of the adhesive force after ultraviolet irradiation in the case of performing UV irradiation treatment is referred to as an adhesive force ratio after ultraviolet irradiation. When the adherend is referred to as glass, the adhesive force ratio after the ultraviolet irradiation of the adhesive film, particularly the surface protection film, which affects one embodiment of the present invention (the glass adhesive force ratio after ultraviolet irradiation) is not particularly limited, but is preferably 1.2 or less ( Lower limit 0).

The peel-to-voltage of the adhesive film according to one embodiment of the present invention is not particularly limited. The absolute value of the peeling versus voltage is preferable as the value is smaller from the viewpoint that the adhesive film after peeling is not charged and has excellent workability. It is preferable that the absolute value of peeling versus voltage of the pressure-sensitive adhesive film according to one embodiment of the present invention, particularly the surface protection film, is 10 kV or less. Further, the absolute value is more preferably 2 kV or less, and even more preferably 0.5 kV or less. Further, the absolute value is more preferably 0.3 kV or less, and particularly preferably 0.2 kV or less (lower limit 0 kV). On the other hand, peeling versus voltage can be measured using a potentiometer, and details of the measuring method are described in Examples.

It is preferable that the adhesive film which concerns on one aspect of this invention has high transparency. Transparency can be evaluated mainly by transmittance and JAV.

The transmittance of the adhesive film according to one embodiment of the present invention is not particularly limited. The transmittance is preferably closer to 100% in view of being able to make the article inspected in a state where the adhesive film is bonded more precisely. The transmittance of the adhesive film according to one embodiment of the present invention, particularly the surface protection film, is preferably 85% or more, and more preferably 90% or more (upper limit 100%). The transmittance can be measured using a haze meter, and details of the measurement method are described in Examples.

The XAG of the adhesive film which concerns on one aspect of this invention is not specifically limited. In view of being able to make the article inspected in a state where the adhesive film is bonded more precisely, the smaller the value is, the better. The adhesive film according to one embodiment of the present invention, in particular, the XABE of the surface protection film is preferably 3% or less, and more preferably 2% or less (lower limit 0%). ＨＡＺＥ can be measured using a haze meter, and details of the measurement method are described in Examples.

The effects of the present invention will be explained using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples.

A thermosetting adhesive composition was prepared according to the following procedure. Hereinafter, preparation and storage of the thermosetting adhesive composition and preparation and evaluation of the surface protection film were all performed in a yellow room shielding ultraviolet rays. In other words, the heat-curable pressure-sensitive adhesive composition and the surface protective film were present under the UV shielding environment from the production until the evaluation was completed, except in the case of intentionally irradiating ultraviolet rays in the following evaluation.

<Preparation of adhesive composition>

[Preparation of thermosetting adhesive composition 1]

(A) Negami Industries Co., Ltd. product name: ART RESIN (registered trademark) @N5500P 100 parts by mass, (B) 35 parts by mass of TMPA as component, Asahi as component (C) Hwasung Co., Ltd. brand name: DURANATE (registered trademark) D101 5.3 parts by mass and Asahi Hwasung Co., Ltd. brand name: DURANATE (registered trademark) E402-80B 3.9 parts by mass, ( D) 1 part by mass of SE-010T manufactured by Negami Industrial Co., Ltd. as component, (I) brand name by IEM RESINGS, as component (E) 1 part by mass of OPM (registered trademark) TPO H, 3M Japan stock as component (F) Company-made product name: 3M (trademark) 2 parts by mass of ion liquid type antistatic agent FC4400 was mixed to prepare a thermosetting adhesive composition 1. Then, ethyl acetate was added so that the concentration of the thermosetting pressure-sensitive adhesive composition (the concentration of the total amount of each component) was 50% by mass, to prepare a pressure-sensitive adhesive composition solution 1.

[Preparation of thermosetting adhesive compositions 2 to 23]

In the production of the thermosetting pressure-sensitive adhesive composition 1, the type and addition amount of each component were changed as described in Tables 1 to 4 below to prepare each thermosetting pressure-sensitive adhesive composition. Then, each pressure-sensitive adhesive composition solution was prepared in the same manner as in the production of the thermosetting pressure-sensitive adhesive composition 1.

The formulation of each thermosetting adhesive composition is shown in Tables 1 to 4 below. In the table, the NCO group represents an isocyanate group. On the other hand, in Tables 1 to 4 below, details of each component are shown below. In addition, the components not described in Table 4 were not used in the preparation of each thermosetting adhesive composition described in Table 4.

[(A) component: Urethane prepolymer having two or more hydroxyl groups]

A1: ART RESIN (registered trademark) ＵN5500P (a urethane prepolymer having a hydroxyl group on both ends, an acryloyloxy group on the side chain and a polyether skeleton at the same time), manufactured by Negami Industries, Ltd.;

[(B) component: polyfunctional (meth)acrylate]

B1: TPMTA (trimethylolpropane triacrylate, hydroxyl value 0 mｇＫOｇＫ/g).

[(C) component: crosslinking agent]

C1: DURANATE (registered trademark) D101 (bifunctional isocyanate (ＨDI)), manufactured by Asahi Chemical Co., Ltd.;

C2: DURANATE (registered trademark) E402-80B (elastic trifunctional isocyanate), manufactured by Asahi Chemical Co., Ltd.;

C3: PAROIL (registered trademark) TCP (peroxy bicarbonate (4-t-butylcyclohexyl)), manufactured by Ilyu Corporation.

[(D) component: crosslinked particles]

D1: SE-010T ((meth)acrylic crosslinked particles, acrylic crosslinked beads, average particle size: 10 μm), manufactured by Negami Industries, Ltd.;

D2: SEE-020T ((meth)acrylic crosslinked particles, acrylic crosslinked beads, average particle diameter of 19 μm), manufactured by Negami Industries, Ltd.;

D3: X-52-854 (silicone-based crosslinked particles, silicone resin powder, average particle diameter of 0.7 µm), manufactured by Shin-Etsu Chemical Co., Ltd.

[(E) component: Photo radical initiator]

E1: OmniRard (registered trademark) TPO H (2,4,6-trimethylbenzoyl-diphenylphosphine oxide), manufactured by IMM Rs Seins.

[(F) component: Antistatic agent]

F1: 3M (trademark) ionic liquid antistatic agent CC4400 (tri-n-butylmethylammonium bistrifluoromethanesulfonimide), manufactured by 3M Japan Corporation.

[(G) Ingredient: Stabilizer]

G1:Irｇanonｘ (registered trademark) 1010 (pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], hindered phenolic antioxidant), JABS Japan Corporation-made;

G2:Tionnium (registered trademark) 292 (bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4- Piperidinyl) mixture of sebacate, hindered amine light stabilizer (BALS), manufactured by BASF Japan Inc.

<Production of surface protection film (adhesive film)>

[Production of surface protection film 1]

A polyethylene terephthalate (PET) film having a thickness of 75 μm, which was subjected to an A treatment (antistatic treatment) on one side, was prepared. The prepared pressure-sensitive adhesive composition solution was applied to the surface of the PET film on the side opposite to the side of the A treatment surface such that the thickness after drying was 75 μm. Then, the coated film on the PET film was dried in a hot air circulation oven at 120° C. for 5 minutes to form an adhesive layer on the PET film. Subsequently, on the surface of the pressure-sensitive adhesive layer (the surface opposite to the surface on the PET film side), a release film (DIA FOIL (registered trademark) MRＦ38 (the surface of the PET film with a thickness of 38 μm treated with a silicone release agent), Mitsubishi Resin Co., Ltd.) was joined. Thereafter, the laminate in which the PET film, the pressure-sensitive adhesive layer, and the release film were laminated in this order was left for 7 days under a test environment of 23° C.×50% RV to prepare a surface protective film 1.

[Production of surface protection films 2 to 23]

In the preparation of the surface protection film 1, each surface protection film was produced in the same manner except that the pressure-sensitive adhesive composition solution 1 was changed to the pressure-sensitive adhesive composition solutions 2 to 23.

<Evaluation 1 of surface protection film>

The following evaluation was performed about the surface protection films 1-18 manufactured above. Each evaluation result is shown in Table 1, Table 2, and Table 3 below.

[Glass adhesion (adhesiveness)]

The surface protective film obtained above was cut into a width of 25 mm and a length of 200 mm. Subsequently, the surface of the pressure-sensitive adhesive layer of the surface protective film after peeling the release film and the alkali-free glass (EAFLEE (registered trademark), manufactured by Corrion Inc.) were pressed. Pressing was performed using a rubber roll having a mass of 2000 g (coated with a rubber layer having a thickness of 6 mm, a width of 45 mm, a roll of 95 mm in diameter (including a rubber layer), and a spring hardness of 80 Ｈs on the roll surface). After crimping, after standing for 3 hours, the strength when the surface protective film was peeled from the alkali-free glass was measured. The strength was measured using a tensile tester (TA.XT plus, Stable Micro systems) under a test environment of 23° C.×50% R%, and a surface protection film from alkali-free glass in the direction of 180° at a peel rate of 2400 mm/min. It was set as the condition of peeling. And the value obtained by the said measurement was made into the glass adhesive force (g/25mm) of the surface protection film. On the other hand, it was said that the glass adhesive strength is good when it is 5 g/25 mm or more and 20 g/25 mm or less.

[Glass adhesion after ultraviolet irradiation (rework property)]

The surface protective film obtained above was cut into a width of 25 mm and a length of 200 mm. Subsequently, the surface of the pressure-sensitive adhesive layer of the surface protective film after peeling the release film and the alkali-free glass (EAVLEE (registered trademark), manufactured by Kornion Co.) were pressed in the same manner as in the evaluation of the glass adhesion. After crimping, after standing for 3 hours, the surface protective film was irradiated with ultraviolet rays to pass through the PET film from the PET film side, and the adhesive layer was cured. The ultraviolet irradiation was conducted under a test environment of 23° C.×50% RV, using a metal halide lamp, and the conditions were 300 mV/cm ² . Thereafter, the glass adhesive force was measured in the same manner as the measurement of the glass adhesive force. This value was called the glass adhesive force (g/25 mm) after ultraviolet irradiation of the surface protection film. The glass adhesive strength after ultraviolet irradiation was not particularly limited as long as it was lower than the value of the glass adhesive strength, but was said to be particularly good when it was less than 5 g/25 mm.

[Bunching workability (frequency of dropping of the adhesive layer)]

The peeling film was peeled from the surface protection film obtained above. Next, the scratch hardness test method of JIS K5600-5-4:1999 base material was referred to, and the presence or absence of adhesive residue (residue) was confirmed. Specifically, the presence or absence of occurrence of pressure-sensitive adhesive residue (residue) when the pens with a sharp tip of 1 mmφ was pressed onto a surface of the pressure-sensitive adhesive layer at a load of 500 g and 1000 g at an angle of 45° and sliding 2 cm. On the other hand, as the degree of occurrence of the adhesive residue (residue) in the test, it was confirmed that the tendency for the occurrence frequency of the adhesive layer to fall off during punching corresponds. For this reason, the test result can be used as an index of punching workability. The punching processability of the surface protective film was evaluated according to the following criteria, and the following Δ evaluation or higher was said to be a good result:

(Evaluation standard)

◎: At 1000 g load, no adhesive residue (residue) was generated.

○: At 1000 g load, the adhesive residue (residue) was generated, but at the 500 g load, the adhesive residue (residue) did not occur.

(Triangle|delta): Under 500 g load, the adhesive residue (residue) generate|occur|produced in a part of adhesive layer,

X: At a load of 500 g, adhesive residue (residue) was generated on the entire surface of the adhesive layer.

[Peeling versus voltage]

In the same manner as in the measurement of the above-mentioned glass adhesive force, the surface protection film and alkali-free glass (EAFLEE (registered trademark), manufactured by CORNERIN Co., Ltd.) were pressed. After crimping, after standing for 3 hours, the surface protective film was peeled from the alkali-free glass in the same manner as in the measurement of the glass adhesive force. At this time, the potential of the surface protective film generated at the time of peeling was measured. For the measurement of the electric potential, an electric potential measuring instrument (STATRION (registered trademark) DK4, manufactured by Shiseido Electrostatics Co., Ltd.) fixed at a position 30 mm high from the center of the film under a test environment of 23°C and 50% RV. The value obtainable by the measurement was referred to as peel-off voltage of the surface protection film. On the other hand, the smaller the value of peel-to-voltage, the better.

[Substance contamination]

Adhesive manufactured by Soken Chemical Co., Ltd. Product name: SDYN (registered trademark) 2137 and cross-linking agent Soken Chemical Co., Ltd. Product name: TD-75, additive Soken Chemical (綜硏A Chemical Co., Ltd. product name: A-50 was added to ethyl acetate as a solvent at a solid ratio of 100/0.1/0.1 (mass ratio) to prepare a solution. Then, using the solution obtained, a product name manufactured by Tongyang Co., Ltd. as the base: Cosmo Shine (registered trademark) A4300 (polyester film, 75 μm thick), and a pressure-sensitive adhesive layer so that the film thickness after drying becomes 25 μm. Formed. Subsequently, a peeling film made of Fujimori Industrial Co., Ltd., a peeling PET 38E0010ＢＧ, which was a peeling film, was pasted to the surface of the pressure-sensitive adhesive layer opposite to the substrate side. Thereafter, the obtained laminate of the base material/adhesive layer/release film was aged for one week at room temperature to prepare an adhesive sheet.

In the same manner as in the measurement of the glass adhesive force, the surface protective film and the alkali-free glass (EAVLEE (registered trademark), manufactured by CORNERIN Co.) were pressed. And after leaving for 2 weeks in an environment of 40 degreeC, it was made the same as the measurement of the said glass adhesive force, and the surface protection film was peeled from the alkali free glass.

Subsequently, the above-mentioned adhesive sheet was press-bonded to the peeling surface of the alkali free glass after peeling the surface of (i) a new alkali free glass and (ii) the surface protection film. Pressing was performed using a rubber roll having a mass of 2000 g (coated with a rubber layer having a thickness of 6 mm, a width of 45 mm, a roll of 95 mm in diameter (including a rubber layer), and a spring hardness of 80 Ｈs on the roll surface). Subsequently, the strength at the time of peeling the adhesive sheet from the alkali-free glass in these was measured respectively. The strength was measured under a test environment of 23° C.×50% RV using a tensile tester, and was set as a condition for peeling the adhesive sheet from the alkali-free glass in the direction of 180° at a peeling rate of 300 mm/min. Then, the ratio of the strength (g/25mm) of peeling the pressure-sensitive adhesive sheet from the alkali-free glass after peeling the surface protection film to the strength (g/25mm) of peeling the pressure-sensitive adhesive sheet from the new alkali-free glass ( %). Then, the glass contamination of the surface protective film was evaluated according to the following criteria, and the following Δ evaluation or higher was said to be a good result:

(Evaluation standard)

◎: The ratio of the strength (g/25mm) when the pressure-sensitive adhesive sheet was peeled from the alkali-free glass after the surface protective film was peeled is 90% or more,

○: The ratio of the strength (g/25mm) when the pressure-sensitive adhesive sheet was peeled from the alkali-free glass after peeling the surface protection film was 80% or more and less than 90%,

(Triangle|delta): The ratio of the strength (g/25mm) when peeling an adhesive sheet from an alkali free glass after peeling a surface protection film is 70% or more and less than 80%,

X: The ratio of the strength (g/25mm) when peeling the pressure-sensitive adhesive sheet from the alkali-free glass after peeling the surface protection film is less than 70%.

[Wetting test]

Wetting was measured at 25°C. The surface protective film obtained above was cut into a width of 25 mm and a length of 200 mm. Then, the surface of the pressure-sensitive adhesive layer (2 in FIG. 1) of the surface protective film (FIG. 1) after peeling the release film and an alkali-free glass (EAFLEE (registered trademark), manufactured by Kornyn Co., Ltd. (3 in FIG. 1)) Touch the edge surface (width 25mm, length 5mm) of one direction of the surface protection film with the alkali-free glass so that the angle between the length direction of the surface protection film and the surface of the alkali-free glass is 20° to 30°. Caught with. Thereafter, the hands were removed from the surface protection film, and the surface protection film and the alkali-free glass were joined only by the gravity of the surface protection film itself (arrow in FIG. 1). The time at which the surface of the pressure-sensitive adhesive layer of the surface protection film at this time spreads to the surface of the alkali-free glass was measured by visual inspection. Then, the wettability of the surface protective film was evaluated according to the following criteria, and the following Δ evaluation or higher was said to be a good result:

(Evaluation standard)

◎: the wet spreading time was less than 3 seconds,

○: wet spreading time of 3 seconds to less than 5 seconds,

△: wet spreading time of 5 seconds or more but less than 10 seconds,

X: The wet spreading time is 10 seconds or more.

[Transmittance (%)]

The obtained surface protection film was cut to a width of 25 mm and a length of 50 mm, and the release film was peeled off. Next, a test sample was prepared by pressing the surface protection film onto an alkali-free glass so that the surface of the pressure-sensitive adhesive layer of the surface protection film was contacted with an alkali-free glass (EAVLEE (registered trademark), manufactured by Kornyn Co., Ltd.). The transmittance (%) of this test sample was measured using a haze meter (NDD500W, manufactured by Nippon Color Industries, Ltd.).

[ＨＡＺＥ（%）]

The obtained surface protection film was cut to a width of 25 mm and a length of 50 mm, and the release film was peeled off. Next, a test sample was prepared by pressing the surface protection film onto an alkali-free glass so that the surface of the pressure-sensitive adhesive layer of the surface protection film was contacted with an alkali-free glass (EAVLEE (registered trademark), manufactured by Kornyn Co., Ltd.). The XAE (%) of this test sample was measured using a haze meter (NDD500W, manufactured by Nippon Electric Industries, Ltd.).

(Table 1 and Table 2) Prescription of each thermosetting adhesive composition and evaluation results of each surface protective film

Surface protection film number One 2 3 4 5 6 (A) Ingredient A1 (parts by mass) 100 100 100 100 100 100 (C) Ingredient C1 (parts by mass) 5.3 5.3 8.8 8.8 3.5 3.5 C2 (parts by mass) 3.9 2.3 3.9 2.3 3.5 2.3 C3 (parts by mass) 0 0 0 0 0.7 0.5 (B) Ingredient B1 (parts by mass) 35 35 50 50 50 35 (E) Ingredient E1 (parts by mass) One One One One One One (F) Ingredient F1 (parts by mass) 2 2 2 2 2 2 (D) Ingredient D1 (parts by mass) One 3 5 0 0 0 D2 (parts by mass) 0 0 0 One 3 0 D3 (parts by mass) 0 0 0 0 0 0.05 Equivalent ratio of the total amount of NCO groups in component (C) to the total amount of hydroxyl groups in component (A) (NCO (total) (mole)/OH (mole)) 2.01 1.80 3.00 2.79 1.45 1.29 (C) Equivalent ratio of the NCO group content of the bifunctional isocyanate to the total amount of NCO groups of the component (NCO (bifunctional) (molar)/NCO (total) (molar)) 0.75 0.83 0.83 0.89 0.68 0.77 Glass adhesion (g/25mm) 11.2 9.8 12.5 13.2 10.2 8.2 Glass adhesion after UV irradiation (g/25mm) 3.7 3.4 2.7 3.4 2.6 2.1 Punchability ◎ ◎ ○ ○ ○ ○ Peel-to-voltage (kV) 0.15 0.12 0.11 0.20 0.15 0.12 Substance contamination ○ ◎ ◎ ○ ○ ○ Wettability ○ ○ ◎ ○ ◎ ◎ Transmittance (%) 91.6 91.3 91.4 91.5 91.7 91.9 Haze (%) 1.5 2.2 2.6 1.8 2.7 1.4 Reference Example

Surface protection film number 7 8 9 10 11 12 (A) Ingredient A1 (parts by mass) 100 100 100 100 100 100 (C) Ingredient C1 (parts by mass) 12.4 12.4 8.8 5.3 8.8 0 C2 (parts by mass) 3.9 3.9 3.9 3.9 0 3.9 C3 (parts by mass) 0 0 One 0.5 0 0 (B) Ingredient B1 (parts by mass) 35 50 50 35 35 35 (E) Ingredient E1 (parts by mass) One One One One One One (F) Ingredient F1 (parts by mass) 2 2 2 2 2 2 (D) Ingredient D1 (parts by mass) 0 0 3 0 One One D2 (parts by mass) 0 0 0 One 0 0 D3 (parts by mass) 0.1 0.25 0 0 0 0 Equivalent ratio of the total amount of NCO groups in component (C) to the total amount of hydroxyl groups in component (A) (NCO (total) (mole)/OH (mole)) 4.02 4.02 3.00 2.01 2.49 0.51 (C) Equivalent ratio of the NCO group content of the bifunctional isocyanate to the total amount of NCO groups of the component (NCO (bifunctional) (molar)/NCO (total) (molar)) 0.87 0.87 0.83 0.75 1.00 0 Glass adhesion (g/25mm) 9.2 8.5 12.5 13.2 15.4 16.8 Glass adhesion after UV irradiation (g/25mm) 2.4 1.9 2.2 2.5 3.2 3.5 Punchability ◎ ◎ ◎ ◎ ◎ △ Peel-to-voltage (kV) 0.11 0.12 0.11 0.18 0.09 0.11 Substance contamination ◎ ○ ○ ○ △ ○ Wettability ◎ ◎ ○ ○ ○ ○ Transmittance (%) 91.9 92.1 91.1 91.4 91.4 91.2 Haze (%) 1.7 2.7 2.4 1.9 1.5 1.4 Reference Example

(Table 3) Prescription of each thermosetting adhesive composition and evaluation results of each surface protective film

Surface protection film number 13 14 15 16 17 18 (A) Ingredient A1 (parts by mass) 100 100 100 100 100 100 (C) Ingredient C1 (parts by mass) 5.3 5.3 5.3 5.3 3.5 3.5 C2 (parts by mass) 3.9 3.9 3.9 3.9 3.5 19.2 C3 (parts by mass) 0 0.5 0 0 0.7 0 (B) Ingredient B1 (parts by mass) 35 35 35 35 50 35 (E) Ingredient E1 (parts by mass) One One One One One One (F) Ingredient F1 (parts by mass) 2 2 2 2 2 2 (D) Ingredient D1 (parts by mass) 12 0 0 0 0 12 D2 (parts by mass) 0 12 0 0 0 0 D3 (parts by mass) 0 0 13 0 0 0 Equivalent ratio of the total amount of NCO groups in component (C) to the total amount of hydroxyl groups in component (A) (NCO (total) (mole)/OH (mole)) 2.01 2.01 2.01 2.01 1.45 3.51 (C) Equivalent ratio of the NCO group content of the bifunctional isocyanate to the total amount of NCO groups of the component (NCO (bifunctional) (molar)/NCO (total) (molar)) 0.75 0.75 0.75 0.75 0.68 0.28 Glass adhesion (g/25mm) 5.2 4.6 3.6 22.3 24.2 3.6 Glass adhesion after UV irradiation (g/25mm) 1.9 2.1 1.9 6.2 5.8 1.2 Punchability △ △ △ ◎ ◎ Ⅹ Peel-to-voltage (kV) 0.20 0.15 0.12 0.15 0.12 0.11 Substance contamination ○ ○ ○ ○ ○ ○ Wettability Ⅹ Ⅹ Ⅹ ○ ○ Ⅹ Transmittance (%) 90.2 90.8 89.1 91.3 92.1 90.2 Haze (%) 7.8 10.2 21.0 1.2 1.1 7.8 Reference Comparative example

As shown in Table 1, Table 2 and Table 3, the surface protective films 13 to 18 have adhesive layers formed from the thermosetting adhesive compositions 13 to 18 according to Comparative Examples outside the scope of the present invention. In these thermosetting adhesive compositions, the amount of the component (D) added is excessive or does not contain the component (D). In addition, it was confirmed that the surface protection films 13 to 15 and 18 had poor punchability and wettability, and high haze. In addition, it was confirmed that the surface protective films 16 and 17 had large glass adhesion.

On the other hand, the surface protective films 1 to 12 have pressure-sensitive adhesive layers formed from the thermosetting pressure-sensitive adhesive compositions 1 to 12 according to the examples within the scope of the present invention. It was confirmed that these surface protection films 1 to 12 were compatible with high adhesion and rework properties. In addition, it was confirmed that these surface protective films are unlikely to cause the pressure-sensitive adhesive layer to fall off, the peeling voltage is small, the substrate contamination is reduced, and the wettability is good. In addition, it was confirmed that these surface protective films have high transmittance and low BAE and high transparency.

<Evaluation 2 of surface protection film>

With respect to the prepared surface protection films 19 to 23, glass adhesion, glass adhesion after ultraviolet irradiation, punchability, peel-to-voltage, substrate contamination, wettability test, transmittance by the same method and evaluation criteria as evaluation 1 of the surface protection film And haze. In addition, the following evaluation was performed about the surface protection films 1 and 19-23 manufactured above in addition to these. Each evaluation result is shown in Table 4 below.

[Glass adhesion ratio]

The surface protective film obtained above was cut into a width of 25 mm and a length of 200 mm. Subsequently, the surface of the pressure-sensitive adhesive layer of the surface protective film after peeling the release film and the alkali-free glass (EAVLEE (registered trademark), manufactured by Kornion Co.) were pressed in the same manner as in the evaluation of the glass adhesion. Subsequently, the alkali-free glass with which the surface protection film was pressed was left for 15 days (360 hours) in a test environment under 23°C x 50% RV and LED illumination (500L uｘ). Thereafter, the strength when the surface protective film was peeled from the alkali-free glass in the same manner as in the evaluation of the glass adhesion was measured, and this value was referred to as the glass adhesion (g/25 mm) after the LED stability test. The value obtained by dividing the value of the glass adhesive force after the LED stability test by the value of the glass adhesive force evaluated above was referred to as the glass adhesive force ratio. Although the glass adhesive force ratio is not specifically limited, it was said that it is especially favorable in the case of 0.8 or more and 1.2 or less.

[The ratio of glass adhesion after ultraviolet irradiation]

The surface protective film obtained above was cut into a width of 25 mm and a length of 200 mm. Subsequently, the surface of the pressure-sensitive adhesive layer of the surface protective film after peeling the release film and the alkali-free glass (EAVLEE (registered trademark), manufactured by Cornion) were pressed in the same manner as in the evaluation of the glass adhesion. Subsequently, the alkali-free glass with which the surface protection film was pressed was left for 15 days (360 hours) in a test environment under 23°C x 50% RV and LED illumination (500L uｘ). Then, the surface protective film after standing was irradiated with ultraviolet rays in the same manner as in the evaluation of the glass adhesive strength after the ultraviolet irradiation, and the adhesive layer was cured. Thereafter, the glass adhesive force was measured in the same manner as the measurement of the glass adhesive force. This value was referred to as glass adhesion (g/25 mm) after UV irradiation after the LED stability test. The value obtained by dividing the value of the glass adhesive strength after ultraviolet irradiation after the LED stability test by the value of the glass adhesive strength after ultraviolet irradiation evaluated above was referred to as the ratio of the glass adhesive strength after ultraviolet irradiation. The ratio of the glass adhesion after ultraviolet irradiation was not particularly limited, but it was said to be particularly good when it was 1.2 or less.

Surface protection film number 19 20 21 One 22 23 (A) Ingredient A1 (parts by mass) 100 100 100 100 100 100 (C) Ingredient C1 (parts by mass) 5.3 5.3 5.3 5.3 5.3 5.3 C2 (parts by mass) 3.9 3.9 3.9 3.9 3.9 3.9 (B) Ingredient B1 (parts by mass) 35 35 35 35 35 35 (E) Ingredient E1 (parts by mass) One One One One One One (F) Ingredient F1 (parts by mass) 2 2 2 2 2 2 (D) Ingredient D1 (parts by mass) One One One One One One (G) Ingredient G1 (parts by mass) 0.05 0.5 0 0 5.3 0 G2 (parts by mass) 0 0 0.1 0 0 5.3 Equivalent ratio of the total amount of NCO groups in component (C) to the total amount of hydroxyl groups in component (A) (NCO (total) (mole)/OH (mole)) 2.01 2.01 2.01 2.01 2.01 2.01 (C) Equivalent ratio of the NCO group content of the bifunctional isocyanate to the total amount of NCO groups of the component (NCO (bifunctional) (molar)/NCO (total) (molar)) 0.75 0.75 0.75 0.75 0.75 0.75 Glass adhesion (g/25mm) 11.1 11.7 11.3 11.2 13.4 14.2 Glass adhesion after UV irradiation (g/25mm) 3.8 3.9 3.4 3.7 6.4 7.2 Glass adhesion ratio 1.0 1.0 1.0 0.7 1.0 1.0 Ratio of adhesion of glass after UV irradiation 1.0 0.9 1.1 1.4 1.1 1.1 Punchability ◎ ◎ ◎ ◎ △ △ Peel-to-voltage (kV) 0.14 0.12 0.15 0.15 0.12 0.11 Substance contamination ○ ○ ○ ○ ○ ○ Wettability ○ ○ ○ ○ ○ ○ Transmittance (%) 91.6 91.3 91.4 91.6 91.1 90.8 Haze (%) 1.6 1.7 1.5 1.5 1.7 1.8 Reference Example

As shown in the results of Table 4, the surface protective films 19 to 23 have pressure-sensitive adhesive layers formed from the pressure-sensitive adhesive compositions 19 to 23 according to the examples within the scope of the present invention. These adhesive compositions contain (G) component. Then, the surface protective films 19 to 23 were in a range in which the ratio of the glass adhesive force and the glass adhesive force after ultraviolet irradiation were better than those of the surface protective film 1 containing no stabilizer. Thereby, it was confirmed that the surface protective films 19 to 23 contain the component (G), and the progress of the photocuring reaction of the pressure-sensitive adhesive layer under LED lighting was suppressed.

These results indicate that the surface protective film affecting one embodiment of the present invention further contains the component (G), so that when stored, no shading is necessary, and storage performance is further improved.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

1: surface protection film after peeling a peeling film
2: Adhesive layer surface
3: alkali free glass

Claims (15)

(A) component: urethane prepolymer having two or more hydroxyl groups,
(B) component: polyfunctional (meth)acrylate,
(C) Ingredient: Crosslinking agent,
(D) component: crosslinked particles,
(E) component: photo-radical initiator, and
(F) Ingredient: Antistatic agent
Containing,
The content of the component (D) relative to 100 parts by mass of the component (A) is 0.01 parts by mass or more and 10 parts by mass or less.
The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive composition of the pressure-sensitive adhesive composition is lowered by light irradiation.
The content of the component (B) with respect to 100 parts by mass of the component (A) is 10 parts by mass or more and 150 parts by mass or less, and the hydroxyl value of the component (B) is 100 mg. Characterized in that the pressure-sensitive adhesive composition.
The method according to claim 1, wherein the component (C) comprises a compound having an isocyanate group,
The pressure-sensitive adhesive composition, wherein the equivalent ratio of the total amount of isocyanate groups of the compound having the isocyanate group to the total amount of hydroxyl groups of the component (A) (NCO (total) (mol)/O(mole)) is 0.2 or more and 10 or less.
The method according to claim 1, wherein the component (C) comprises a compound having an isocyanate group,
The compound having an isocyanate group includes a bifunctional isocyanate,
The pressure-sensitive adhesive composition, characterized in that the equivalent ratio of the isocyanate group content of the bifunctional isocyanate to the total amount of isocyanate groups of the isocyanate (NCO (bifunctional) (molar) / NCO (total) (molar)) is greater than 0 and less than 1.
According to claim 1, wherein the component (C) is a pressure-sensitive adhesive composition, characterized in that it comprises a trifunctional or higher isocyanate.
The pressure-sensitive adhesive composition according to claim 1, wherein the component (A) contains a urethane prepolymer having a polyether skeleton and two or more hydroxyl groups.
8. The pressure-sensitive adhesive composition according to claim 7, wherein the urethane prepolymer having a polyether skeleton and two or more hydroxyl groups is a urethane prepolymer having a polyether skeleton and two or more hydroxyl groups and (meth)acryloyloxy groups.
The pressure-sensitive adhesive composition according to claim 1, wherein the average particle diameter of the component (D) is 0.5 μm or more and 30 μm or less.
The pressure-sensitive adhesive composition according to claim 1, wherein the content of the component (E) relative to 100 parts by mass of the component (A) is 0.1 parts by mass or more and 10 parts by mass or less.
The pressure-sensitive adhesive composition according to claim 1, wherein the content of the component (F) relative to 100 parts by mass of the component (A) is 0.5 parts by mass or more and 10 parts by mass or less.
The adhesive composition according to claim 1, further comprising (G) component: a stabilizer.
The pressure-sensitive adhesive composition according to claim 1, wherein the (A) component does not contain more than 5 parts by mass of the (G) component: stabilizer.
Hardened|cured material of the adhesive composition of any one of Claims 1-13.
A surface protective film comprising a resin film and an adhesive layer composed of the cured product of claim 14 disposed on one surface of the resin film.

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