JP2016125061A - Slight adhesive composition, adhesiveness-reducing agent, and adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new technology capable of imparting slight adhesiveness and repeelability to a (meth)acrylic adhesive without using a silicone compound.SOLUTION: A slight adhesive composition contains a (meth)acrylic adhesive resin, a nitrogen-containing compound, and ion-bonding salt represented by the following formula (1). In the formula (1), Qis a cation derived from a silane compound containing an amino group or an imino group; and Tis a sulfate ester anion, phosphate ester anion or sulfonic acid anion.SELECTED DRAWING: None

Description

  The present invention relates to a slightly pressure-sensitive adhesive composition, a tackiness reducing agent, and a pressure-sensitive adhesive sheet.

  In the electronic industry field, when an electronic device (component) is manufactured, transported, used, or the like, an adhesive film (protective film) is attached to the surface of the electronic device (component).

  In particular, highly functional terminals called smartphones are rapidly spreading, and many of them are operated by touching a display called a touch panel. Similarly, there is a tablet terminal equipped with a touch panel display, which is a computer mainly intended to be carried. With the spread of these, adhesive films for screen protection have been widely used.

  The pressure-sensitive adhesive used for the above-mentioned pressure-sensitive adhesive film is required to have slight tackiness (that can be peeled off with a small force) and re-peelability (which can be peeled cleanly even after being applied once). There are (meth) acrylic adhesives, rubber-based adhesives, silicone-based adhesives, etc. as such adhesives, but (meth) acrylic adhesives can be manufactured relatively inexpensively. The demand for agents is increasing.

  As the above (meth) acrylic pressure-sensitive adhesive with the slight adhesiveness and removability in mind, for example, in Patent Document 1, a pressure-sensitive adhesive composition containing (meth) acrylic pressure-sensitive adhesive resin, dimethylpolysiloxane and a suitable crosslinking agent Things have been proposed. Patent Document 2 and Patent Document 3 propose a pressure-sensitive adhesive composition containing a (meth) acrylic pressure-sensitive adhesive resin and polysiloxane having an oxyalkylene chain.

JP 07-33210 A JP 2009-292959 A JP 2013-237827 A

  However, as in Patent Document 1, when dimethylpolysiloxane (silicone compound) is added to the (meth) acrylic adhesive resin, white turbidity or phase separation occurs, or the silicone compound contained in the adhesive composition migrates. As a result, the adherend was contaminated. The pressure-sensitive adhesive composition containing polysiloxane (silicone compound) having an oxyalkylene chain disclosed in Patent Documents 2 and 3 also has the same disadvantages as the pressure-sensitive adhesive composition disclosed in Patent Document 1. sell.

  Therefore, there has been a demand for a pressure-sensitive adhesive composition that exhibits excellent fine tackiness and removability without using a silicone compound that may cause problems such as cloudiness, phase separation, and migration.

  Therefore, an object of the present invention is to provide a novel technique capable of imparting fine adhesion and removability to a (meth) acrylic adhesive without using a silicone compound.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, surprisingly, for (meth) acrylic adhesive resins, a nitrogen-containing compound; a cation derived from a silane compound containing an amino group or an imino group, and a sulfate ester anion having a specific structure, phosphorus It has been found that by adding an ion-binding salt composed of an acid ester anion or a sulfonate anion; and (meth) acrylic pressure-sensitive adhesive can be imparted with slight adhesiveness and removability, the present invention has been completed. .

  That is, according to one aspect of the present invention, there is provided a slightly pressure-sensitive adhesive composition containing a (meth) acrylic pressure-sensitive adhesive resin, a nitrogen-containing compound, and an ion-binding salt represented by the following formula (1). R:

In the above formula (1),
Q ⁺ is a cation derived from a silane compound containing an amino group or an imino group;
T ⁻ represents the following formula (t-1):

In the above formula (t-1),
R ¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon An aryl group having 6 to 30 atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms;
A ¹ is a linear or branched alkylene group having 2 to 4 carbon atoms,
s is an integer from 0 to 50,
Sulfate anion represented by
Following formula (t-2):

In the above formula (t-2),
R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms. A group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, wherein R ² and R ³ Is not a hydrogen atom at the same time,
A ² and A ³ are each independently a linear or branched alkylene group having 2 to 4 carbon atoms,
t and u are each independently an integer of 0 to 50;
A phosphate ester anion represented by
The following formula (t-3):

In the above formula (t-3),
R ⁴ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon An aryl group having 6 to 30 atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms;
A ⁴ is a linear or branched alkylene group having 2 to 4 carbon atoms,
v is an integer from 0 to 50,
It is a sulfonate anion shown by.

  Moreover, according to the other form of this invention, the pressure-sensitive adhesive composition containing the (meth) acrylic pressure-sensitive adhesive resin includes the nitrogen-containing compound and the ion-binding salt represented by the formula (1). There is provided a tackiness reducing agent that is added and used to reduce the tackiness of the pressure sensitive adhesive composition.

  According to the present invention, a (meth) acrylic adhesive resin is added with a nitrogen-containing compound; a cation derived from a silane compound containing an amino group or an imino group, and an ion-binding salt comprising a specific anion. By doing so, a novel technique is provided that can impart fine tackiness and removability to a (meth) acrylic pressure-sensitive adhesive without using a silicone compound.

FIG. 1 is a graph showing the change over time of the adhesive strength of the pressure-sensitive adhesive layer formed by the fine pressure-sensitive adhesive compositions according to the present invention, comparative examples and reference examples.

  According to the first aspect of the present invention, there is provided a slightly pressure-sensitive adhesive composition comprising a (meth) acrylic pressure-sensitive adhesive resin, a nitrogen-containing compound, and an ion-binding salt represented by the following formula (1). R:

In the above formula (1),
Q ⁺ is a cation derived from a silane compound containing an amino group or an imino group;
T ⁻ represents the following formula (t-1):

In the above formula (t-1),
R ¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon An aryl group having 6 to 30 atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms;
A ¹ is a linear or branched alkylene group having 2 to 4 carbon atoms,
s is an integer from 0 to 50,
Sulfate anion represented by
Following formula (t-2):

In the above formula (t-2),
R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms. A group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, wherein R ² and R ³ Is not a hydrogen atom at the same time,
A ² and A ³ are each independently a linear or branched alkylene group having 2 to 4 carbon atoms,
t and u are each independently an integer of 0 to 50;
A phosphate ester anion represented by
The following formula (t-3):

In the above formula (t-3),
R ⁴ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon An aryl group having 6 to 30 atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms;
A ⁴ is a linear or branched alkylene group having 2 to 4 carbon atoms,
v is an integer from 0 to 50,
It is a sulfonate anion shown by.

  Moreover, according to the other form of this invention, the pressure-sensitive adhesive composition containing the (meth) acrylic pressure-sensitive adhesive resin includes the nitrogen-containing compound and the ion-binding salt represented by the formula (1). There is provided a tackiness reducing agent that is added and used to reduce the tackiness of the pressure sensitive adhesive composition.

  According to the techniques disclosed in Patent Documents 1 to 3, since the silicone compound is not highly compatible with the (meth) acrylic adhesive resin, migration of the silicone compound to the adherend in addition to white turbidity and phase separation. It is thought that has occurred. However, on the other hand, since the compatibility between the silicone compound and the (meth) acrylic adhesive resin is not high, in some cases, the silicone compound is arranged on the surface of the (meth) acrylic adhesive resin, and the surface of the adhesive It is also considered that the (meth) acrylic adhesive resin is imparted with slight adhesiveness and removability by coating (or exposing to the surface). Therefore, the pressure-sensitive adhesive composition according to the techniques of Patent Documents 1 to 3 can improve the micro-adhesiveness and removability by utilizing the low compatibility between the silicone compound and the (meth) acrylic pressure-sensitive adhesive resin. On the other hand, it is considered that there is a so-called trade-off problem that white turbidity and phase separation are likely to occur and the silicone compound is likely to migrate to the adherend.

  On the other hand, the present inventors have taken into consideration the above-described problem (providing means capable of imparting slight adhesiveness and removability to a (meth) acrylic adhesive without using a silicone compound). , Earnest research. As a result, with respect to the (meth) acrylic adhesive resin, a nitrogen-containing compound and an ion-binding salt represented by the above formula (1) (hereinafter sometimes simply referred to as “ion-binding salt (1)”) It has been found that by adding, a (meth) acrylic pressure-sensitive adhesive is imparted with slight adhesion and removability. The mechanism is not clear, but is presumed as follows.

The ion-binding salt (1) used in the present invention has a cation derived from a silane compound containing an amino group or an imino group as a cation (Q ⁺ ). It is considered that silicon atoms (Si) contained in such cations are arranged so as to be exposed on the surface of the resin when added to the (meth) acrylic adhesive resin due to the interfacial energy. On the other hand, the amino group or imino group contained in the cation (Q ⁺ ) (particularly, the cation moiety generated by positively charging these substituents) and / or the anion (T ⁻ ) of the ion-binding salt (1) On the other hand, when the nitrogen-containing compound interacts, the ion-binding salt (1) is partially taken into the (meth) acrylic adhesive resin and fixed near the surface of the resin. At this time, since the nitrogen-containing compound has a high affinity with the (meth) acrylic adhesive resin, the ion-binding salt (1) is easily adapted to the (meth) acrylic adhesive resin, and is also fixed to the resin. It is estimated that (anchor effect) is achieved.

  Therefore, as described above, in the slightly pressure-sensitive adhesive composition of the present invention, the silicon atom contained in the cation of the ion-binding salt (1) covers the surface of the (meth) acrylic pressure-sensitive adhesive resin (or is exposed on the surface). In addition, the portion other than the silicon atom is fixed in the (meth) acrylic adhesive resin by the anchor effect of the nitrogen-containing compound. As a result, due to the silicon atoms arranged on the surface of the (meth) acrylic adhesive resin, the original adhesiveness of the (meth) acrylic adhesive resin is reduced, and excellent fine adhesion and removability are exhibited (meta ) An acrylic pressure-sensitive adhesive composition can be obtained. In addition, in the slightly pressure-sensitive adhesive composition of the present invention, as described above, the ion-binding salt (1) is (meth) by the interaction with the nitrogen-containing compound having high affinity with the (meth) acrylic pressure-sensitive adhesive resin. Since it is fixed to the acrylic adhesive resin, it is considered that the ion-binding salt (1) is easily compatible with the resin and is not easily detached. Therefore, the problem concerning migration can be effectively solved.

  Furthermore, the inventors have also surprisingly found that the structure of the present invention can suppress the adhesive force from increasing with time (adhesion progress). The mechanism is that the ion-binding salt (1) localized and immobilized on the surface layer of the (meth) acrylic pressure-sensitive adhesive composition is changed over time between the (meth) acrylic pressure-sensitive adhesive composition and the adherend. This is considered to suppress an increase in the number of interactions.

  Hereinafter, embodiments of the present invention will be specifically described.

<Slight adhesive composition>
The slightly pressure-sensitive adhesive composition according to the present invention includes a (meth) acrylic pressure-sensitive adhesive resin, a nitrogen-containing compound, and an ion-binding salt (1). Hereinafter, each of these components will be described in detail.

[(Meth) acrylic adhesive resin]
As the (meth) acrylic adhesive resin used in the present invention, (meth) acrylic resins obtained by homopolymerizing or copolymerizing various (meth) acrylic acid ester monomers are used.

  Examples of the monomer used for the production of the (meth) acrylic resin include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and methyl (meth). An alkyl group such as acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate ( 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate ) Acrylate, hydroxyl group-containing (meth) acrylate such as 10-hydroxydecyl (meth) acrylate; acrylamide, vinyl alcohol, vinyl acetate, 2-hydroxyethyl vinyl ether, N, N-dimethylaminoethyl (meth) acrylate, N, N- Examples include dimethylaminopropyl (meth) acrylate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl isocyanate, and (meth) acrylic acid. These monomers can be used in appropriate combinations according to the required adhesive properties.

  Further, as the (meth) acrylic adhesive resin, a polymer having a glass transition temperature (Tg) of usually 0 ° C. or lower is preferably used, and the glass transition temperature (Tg) is −100 ° C. to −5 ° C. It is preferable, and it is more preferable that it is -80 degreeC--10 degreeC. In addition, the glass transition temperature (Tg) of a base polymer can be adjusted in the said range by changing the monomer component and composition ratio to be used suitably.

  Furthermore, the (meth) acrylic adhesive resin preferably has a sea-island structure (that is, a microdomain structure) in which a dispersed phase (island) is dispersed in a continuous phase (sea). Since the resin having such a sea-island structure is presumed to have a pseudo-crosslinked structure, partial incorporation of the ion-binding salt (1) into the (meth) acrylic adhesive resin is further strengthened. As a result, it is considered that the effects of the present invention can be further improved.

  As the (meth) acrylic adhesive resin, a synthetic product or a commercially available product may be used. Examples of commercially available products that satisfy the above-mentioned properties include Nippon Shokubai Co., Ltd. ACRESET (registered trademark) AST8918E.

[Ion-binding salt (1)]
The ion-binding salt (1) used in the present invention comprises a cation derived from a silane compound containing an amino group or an imino group and a specific anion. More specifically, as represented by the above formula (1), the ion-binding salt (1) includes a cation (Q ⁺ ) derived from a silane compound containing an amino group or an imino group, and the above formula ( a sulfate ester anion represented by t-1), a phosphate ester anion represented by formula (t-2), or a sulfonate anion (T ⁻ ) represented by formula (t-3).

(Cation Q ⁺ )
In the above formula (1), “a cation derived from a silane compound containing an amino group or an imino group” means that a cation or a carbocation is added to the silane compound containing an amino group or an imino group. Any charged one is acceptable. Therefore, Q ⁺ does not need to be positively charged by adding a proton or the like to the amino group or imino group in the silane compound containing an amino group or imino group, and the proton or the like is added to another cationic group. In this case, it may be positively charged, but from the viewpoint of easy availability, it is preferable that the amino group or imino group is positively charged by adding a proton or the like.

Here, the “silane compound containing an amino group or imino group” means that having at least one silicon atom (Si) and at least one amino group or imino group, and having a silicone skeleton. Anything other than those having (that is, a polysiloxane skeleton having a repeating unit of -Si-O-) can be used. In the above, the amino group is a substituent represented by “—N (R ′) ₂ ”, and the substituent represented by R ′ is not particularly limited, but for example, each independently, Examples include a hydrogen atom, an alkyl group, and an aryl group. The imino group is a substituent represented by “—N═C (R ′) ₂ ”, wherein R ′ is the same as described above. The “silane compound containing an amino group or an imino group” may contain both an amino group and an imino group.

  As such a compound, for example, a silane compound having a substituent containing an amino group (however, a silane compound other than a silicone compound) and a silane compound having a substituent containing an imino group (however, a silane compound other than a silicone compound) ).

  The silane compound having a substituent containing the amino group (however, a silane compound other than a silicone compound) may be any one as long as it has one or more silicon atoms and amino groups as described above. Aminosilane, diaminosilane, triaminosilane, alkylaminosilane, alkyl (alkylamino) silane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, tetrakis (alkylamino) silane, alkyl Tris (alkylamino) silane, dialkylbis (alkylamino) silane, trialkyl (alkylamino) silane, tris (alkylamino) alkoxysilane, bis (alkylamino) dialkoxysila , And (alkylamino) trialkoxysilanes.

  The silane compound having a substituent containing the imino group (however, a silane compound other than a silicone compound) may be any one as long as it has one or more silicon atoms and an imino group as described above. Examples include N-alkyl (trialkylsilyl) alkaneimine, N-alkyl (alkoxydialkylsilyl) alkaneimine, N-alkyl (dialkoxyalkylsilyl) alkaneimine, and N-alkyl (trialkoxysilyl) alkaneimine.

  In the silane compound having a substituent containing an amino group and the silane compound having a substituent containing an imino group, the positional relationship (positional relationship in the molecule) between the amino group or imino group and the silicon atom is not particularly limited. However, it preferably has a silicon atom at one end of the molecular main chain and an amino group or imino group at the other end. If the distance between the amino group or imino group and the silicon atom is too close, the affinity between the (meth) acrylic adhesive resin and the silicon atom is not high. There is a possibility that the affinity with the salt (1) is inhibited and the ion-binding salt (1) is not fixed well. However, by adopting the above-described form, a certain distance can be maintained between the silicon atom and the amino group or imino group, as well as the anion constituting the ion-binding salt (1). As a result, the silicon ends can be arranged at a certain distance from the surface of the (meth) acrylic adhesive resin, so that the ion-binding salt (1) is stably coated on the surface of the (meth) acrylic adhesive resin. can do. Here, the “coating” includes a form in which the ion-binding salt (1) is adsorbed on the surface and a form protruding from the surface.

  Therefore, in view of the preferable form, the silane compound containing an amino group or imino group preferably has a certain size, and its molecular weight is preferably 100 or more, and 150 or more. Is more preferable. On the other hand, the upper limit is not particularly limited, but it is preferably 2000 or less in consideration of substantially available silane compounds (however, excluding silicone compounds).

  As described above, as the silane compound containing an amino group or imino group, a silane compound having a substituent containing an amino group, a silane compound having a substituent containing an imino group, or the like can be used. These compounds can be appropriately selected from the viewpoint of compatibility with the (meth) acrylic pressure-sensitive adhesive resin used in the fine pressure-sensitive adhesive composition, but from the viewpoint of availability, price, etc., a substituent containing an amino group A silane compound having

  Further, in the silane compound having a substituent containing an amino group, the amino group contained in the compound is preferably primary, secondary or tertiary, more preferably primary or secondary, Those that are primary are particularly preferred. A primary to tertiary amine is preferable from the viewpoint of simplifying the reaction process. From such a viewpoint, the silane compound particularly preferably contains a primary amine.

  More specifically, the silane compound having a substituent containing an amino group preferably has the following structure.

That is, the ion binding salt (1) is represented by the above formula (1):
Q ⁺ represents the following formula (q-1):

In the above formula (q-1),
X is —CH ₂ — or an oxygen atom (—O—);
Y is -NH-,
Z is —N (R ⁶ ) ₂ or —N═C (R ⁶ ) ₂ ;
R ⁵ each independently represents a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. Groups, substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy groups having 3 to 20 carbon atoms, substituted or unsubstituted carbon atoms An aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (-OR ⁷ , wherein R ⁷ is a substituted or unsubstituted carbon atom; Represents 6 to 30 aryl groups),
R ⁶ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted Substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, substituted or unsubstituted 6 to 6 carbon atoms 30 aryl groups, or substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms (-OR ⁸ , wherein R ⁸ is substituted or unsubstituted carbon atoms having 6 to 30 carbon atoms. Represents an aryl group of
m is an integer of 0 to 5,
n is an integer of 0 to 5,
q is 0 or 1;
r is 0 or 1;
It is preferable that it is a cation derived from the compound shown by these.

  In the present specification, “substituted or unsubstituted” means that a hydrogen atom of a certain group may be substituted with another group or may not be substituted. Here, the substituent that can be substituted is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms (for example, cyclopentyl group, cyclohexyl group), a hydroxyalkyl group having 1 to 20 carbon atoms (for example, , A hydroxymethyl group, a hydroxyethyl group), an alkoxyalkyl group having 2 to 20 carbon atoms (for example, a methoxyethyl group), an alkoxy group having 1 to 20 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, An isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, a dodecyloxy group, etc., and a cycloalkoxy group having 3 to 20 carbon atoms (for example, a cyclopentyloxy group, cyclohexyloxy group) Group) Alkenyl group, alkynyl group, amino group, aryl group C6-C30 aryloxy group (for example, phenoxy group, naphthyloxy group), C1-C20 alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group) , Dodecylthio group), cycloalkylthio group having 3 to 20 carbon atoms (for example, cyclopentylthio group, cyclohexylthio group), arylthio group having 6 to 30 carbon atoms (for example, phenylthio group, naphthylthio group), 2 carbon atoms To 20 alkoxycarbonyl groups (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group), aryloxycarbonyl groups having 7 to 20 carbon atoms (for example, phenyloxycarbonyl group) Carbonyl group, naphthyloxy group), a hydroxyl group (-OH), carboxyl group (-COOH), a thiol group (-SH), and the like cyano group (-CN) is. The number of substituents that are further substituted for one substituent is not particularly limited, but the number of substituents that are further substituted for one substituent is preferably 3 or less, and 2 or less. More preferably, it is even more preferably 1 or less, and particularly preferably 0. It can be appropriately selected in consideration of the desired effect (given fine adhesion and removability). In the above, they are not substituted with the same substituent. That is, an alkyl group as a substituent is not substituted with an alkyl group.

In the formula (q-1), X is a divalent radical substituted directly on the silicon atom, -CH ₂ - shows a or an oxygen atom (-O-). Here, q represents the number of X and is 0 or 1. Therefore, the substituent represented by X is not necessarily contained.

  In the above formula (q-1), Y represents —NH—. Here, r represents the number of Y and is 0 or 1. Therefore, the substituent (—NH—) represented by Y is not necessarily contained. From the viewpoints of stability of the ion-binding salt (1) and ease of arrangement of the ion-binding salt (1) with respect to the surface of the (meth) acrylic adhesive resin, r = 0, that is, Y does not exist Is preferred. On the other hand, when Y is present, the substituent can be a secondary amino cation, and therefore Y is preferably present from the viewpoint of the stability of the amino cation itself.

In the above formula (q-1), Z is —N (R ⁶ ) ₂ or —N═C (R ⁶ ) ₂ . Since R ⁶ will be described in detail below, detailed description thereof is omitted here. Thus, since the compound represented by the formula (q-1) includes an amino group or imino group as Z, a proton or the like is added to the nitrogen atom in the amino group or imino group, and the compound represented by the formula (q-1) The compounds shown tend to be cations. Therefore, it is suitable for constituting a cation of the ion-binding salt (1).

Here, Z is preferably -N (R ⁶ ) ₂ from the viewpoint of availability and stability of the ion-binding salt (1). At this time, Z is likely to form a stable ammonium ion ([—N (R ⁶ ) ₃ ] ⁺ ) by adding a proton or the like.

In the ammonium ion ([—N (R ⁶ ) ₃ ] ⁺ ), each R ⁶ is independently a hydrogen atom or another substituent (an alkyl group or the like) containing a carbon atom described in detail below. From the viewpoint of making it easier to arrange the ion-binding salt (1) on the surface of the (meth) acrylic adhesive resin, at least one of R ⁶ is a hydrogen atom (ie, Q ⁺ is a primary to tertiary amino acid). Cation), preferably two or more are hydrogen atoms (ie, Q ⁺ is a primary and secondary amino cation), and all three are hydrogen atoms (ie, Q ⁺ is a primary amino cation). Is particularly preferred.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, which are respectively represented as R ⁵ and R ⁶ in the above formula (q-1), include, for example, a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isoamyl group, tert-pentyl group, neopentyl group, n-hexyl group, 3-methyl Pentan-2-yl group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4-methylpentan-2-yl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 3 , 3-dimethylbutan-2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethyl Nyl group, 1- (n-propyl) butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1,1-diethylpropyl group, 1,3,3-trimethylbutyl group, 1-ethyl -2,2-dimethylpropyl group, n-octyl group, 2-methylhexane-2-yl group, 2,4-dimethylpentan-3-yl group, 1,1-dimethylpentan-1-yl group, 2, 2-dimethylhexane-3-yl group, 2,3-dimethylhexane-2-yl group, 2,5-dimethylhexane-2-yl group, 2,5-dimethylhexane-3-yl group, 3,4- Dimethylhexane-3-yl group, 3,5-dimethylhexane-3-yl group, 1-methylheptyl group, 2-methylheptyl group, 5-methylheptyl group, 2-methylheptan-2-yl group, 3- Methylheptane 3-yl group, 4-methylheptan-3-yl group, 4-methylheptan-4-yl group, 1-ethylhexyl group, 2-ethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, 1,1 -Dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1-methylpentyl group, 1-ethyl-4-methylpentyl group, 1,1,4-trimethylpentyl group 2,4,4-trimethylpentyl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1,3,3-tetramethylbutyl group, n-nonyl group, 1-methyloctyl group, 6-methyl Octyl group, 1-ethylheptyl group, 1- (n-butyl) pentyl group, 4-methyl-1- (n-propyl) pentyl group, 1,5,5-trimethylhexyl group, 1,1 5-trimethylhexyl group, 2-methyloctane-3-yl group, n-decyl group, 1-methylnonyl group, 1-ethyloctyl group, 1- (n-butyl) hexyl group, 1,1-dimethyloctyl group, 3,7-dimethyloctyl group, n-undecyl group, 1-methyldecyl group, 1-ethylnonyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, 1-methyltridecyl group, n-pentadecyl group, Examples thereof include linear and branched alkyl groups such as n-hexadecyl group, n-heptadecyl group, n-octadecyl group and n-nonadecyl group. From the viewpoint of availability and ease of arrangement of the ion-binding salt (1) on the surface of the (meth) acrylic adhesive resin, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms is preferable. 2-ethylhexyl group, tridecyl group and 1,2-bis (2-ethylhexyloxycarbonyl) ethyl group are more preferable, and 2-ethylhexyl group is particularly preferable.

Examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, which are respectively represented as R ⁵ and R ⁶ in the formula (q-1), include a methoxy group, an ethoxy group, and a propoxy group. Linear, branched alkoxy groups such as isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group and octyloxy group. From the viewpoint of availability and ease of arrangement of the ion-binding salt (1) with respect to the surface of the (meth) acrylic adhesive resin, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms is more preferred. A methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a 2-ethylhexyloxy group are more preferable.

Examples of the substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, which are respectively represented as R ⁵ and R ⁶ in the formula (q-1), include a cyclopropyl group, a cyclopentyl group, Examples include a cyclohexyl group, a norbornyl group, and an adamantyl group. From the viewpoint of availability and ease of arrangement of the ion-binding salt (1) on the surface of the (meth) acrylic adhesive resin, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms is More preferred are a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, which are respectively represented as R ⁵ and R ⁶ in the above formula (q-1), include a cyclopropyloxy group and a cyclobutyloxy group. Group, cyclopentyloxy group, and cyclohexyloxy group. From the viewpoint of availability and ease of arrangement of the ion-binding salt (1) with respect to the surface of the (meth) acrylic adhesive resin, a substituted or unsubstituted cycloalkoxy group having 1 to 10 carbon atoms is More preferred are a cyclopropyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

Examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms, which are respectively represented as R ⁵ and R ⁶ in the above formula (q-1), include, for example, a phenyl group, a biphenyl group, 1 -Naphtyl, 2-naphthyl, 9-anthryl, 9-phenanthryl, 1-pyrenyl, 5-naphthacenyl, 1-indenyl, 2-azurenyl, 9-fluorenyl, terphenyl, quarterphenyl Group, mesityl group, pentalenyl group, binaphthalenyl group, tannaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthrenyl group Senyl group, quarteranthracenyl group, Nthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group , A coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an obalenyl group, and the like. From the viewpoint of availability and ease of arrangement of the ion-binding salt (1) on the surface of the (meth) acrylic adhesive resin, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms is preferable. , Phenyl group, dimethylphenyl group (2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, etc.), isopropylphenyl group (2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group) and dodecylphenyl group (2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecylphenyl group) are particularly preferable.

The substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, which is represented as R ⁵ and R ⁶ in the above formula (q-1), has the chemical formula “—OR ⁷ ” or “—OR ⁸ ”. In this case, R ⁷ and R ⁸ each independently represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Here, since explanation of R ⁷ and R ^{8 is} the same as that of the above-mentioned aryl group, detailed explanation is omitted here. From the viewpoint of availability and ease of arrangement of the ion-binding salt (1) on the surface of the (meth) acrylic adhesive resin, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms is Preferable are phenoxy group and naphthyloxy group.

M and n in the formula (q-1) each independently represent the number of methylene groups (—CH ₂ —), m is an integer of 0 to 5, and n is an integer of 0 to 5. is there. Therefore, m + n is an integer of 0-10. In the case where Y does not exist (r = 0), the number of methylene groups is synonymous when the value of m + n is the same. For example, m = 1 and n = 2 (m + n = 3) are the same as m = 3 and n = 0, m = 0 and n = 3, and m = 2 and n = 1. The structure of is shown.

  Here, when Y does not exist (r = 0), m + n = 1 to 8 is preferable, and m + n = 1 to 5 is more preferable.

  Moreover, when Y exists (r = 1), it is preferable that it is m + n = 1-8, and it is more preferable that it is 2-6. Here, it is particularly preferable that m = 1 to 3 and n = 1 to 3.

In the formula (q-1), when X is present (q = 1) and X is —CH ₂ —, the number is further defined by the adjacent methylene group (—CH ₂ —: m). Are also synonymous when the values of q + m are the same. Furthermore, when X is present (q = 1) and X is —CH ₂ — and Y is absent (r = 0), these are synonymous when q + m + n values are the same. .

In the formula (q-1), at least one of R ⁵ substituted on the silicon atom is a hydroxy group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or substituted. Alternatively, it is preferably an unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. When at least one of the substituents R ⁵ on silicon is a hydroxy group, an alkoxy group, a cycloalkoxy group, or an aryloxy group, it becomes easy to impart fine tackiness and removability. This can be explained by the following mechanism. That is, the above-described slight adhesion and removability are expressed by the above-mentioned substituents (hydroxy group, alkoxy group, cycloalkoxy group, aryloxy group) being condensed with neighboring silicon atoms by hydrolysis, and-(Si-O This is considered to be due to the formation of a network of -Si)-. More specifically, the nitrogen-containing compound described in detail below serves as a catalyst to promote hydrolysis and polycondensation with water in the atmosphere, and the silicon atom contained in the ion-binding salt (1) is polysiloxane-like. Presumed to form a structure. Thus, the polysiloxane-like structure having the-(Si-O-Si)-network easily imparts fine adhesion and removability. Furthermore, since the said structure is fixed to the (meth) acrylic-type adhesive resin surface, the effect which suppresses migration improves more. In addition to this, the effect of suppressing adhesion progress is further improved.

  Therefore, in the above-mentioned form, “the slightly pressure-sensitive adhesive composition contains an ion-binding salt (1)” means that the ion-binding salt (1) contained in the tackiness reducing agent is polycondensed or (meta ) It also includes the case where it does not remain in the form at the time of addition by reacting with an acrylic adhesive resin or the like. That is, “the fine pressure-sensitive adhesive composition contains the ion-binding salt (1)” means that the fine pressure-sensitive adhesive composition has a molecular structure derived from the compound constituting the ion-binding salt (1). Means that.

Among the compounds represented by the above formula (q-1), the following compounds are preferable from the viewpoint of easily imparting fine tackiness and removability and having a particularly high effect of suppressing migration. That is, the ion-binding salt (1) is represented by the formula (q-1), wherein X is —CH ₂ —, Z is —NH ₂ , and at least one of R ⁵ is substituted with a hydroxy group. A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted carbon atom having 6 to 6 carbon atoms 30 is an aryloxy group, m is an integer of 0 to 3, n is 0, q is 1, and r is 0; a cation Q ⁺ derived from the compound represented by Is preferably included.

Furthermore, among the compounds represented by the formula (q-1), all R ⁵ are preferably a hydroxy group or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. Or an unsubstituted alkoxy group having 1 to 10 carbon atoms. The ion-binding salt (1) containing the cation Q ⁺ derived from such a compound has a high effect of imparting fine tackiness and removability, and has a particularly high effect of suppressing migration. In addition, the effect of suppressing adhesion progress over time can be further improved.

  In the present invention, specific compounds preferably used as the silane compound containing an amino group or imino group include the following compounds.

  For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3- Aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3 -Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and the like.

(Anion T ⁻ )
In the formula (1), the anion (T ⁻ ) is represented by the sulfate anion represented by the formula (t-1), the phosphate anion represented by the formula (t-2), or the formula (t-3). Sulfonate anion. Since these anions are anions having a specific structure, the affinity with the (meth) acrylic pressure-sensitive adhesive resin is improved by interacting with the nitrogen-containing compound, and as a result, the fineness due to the ion-binding salt (1) is improved. This can greatly contribute to imparting tackiness and removability. In addition, these anions provide a counter anion having a structure containing no halogen as the counter anion of the cation, and are therefore suitable for use in applications where halogens are hated. Hereinafter, the structure of these anions will be specifically described.

Linear or branched, each represented as A ¹ in the above formula (t-1), A ² and A ³ in the formula (t-2), and A ⁴ in the formula (t-3). Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group. From the viewpoint of availability, an ethylene group and a propylene group are particularly preferable.

^{R 1} in the formula (t-1) in the formula (t-2) in ^{R 2} and ^{R 3,} and the formula (t-3) represented respectively as ^{R 4} in the, whether or unsubstituted are substituted An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, Since the same as each substituent in the compound represented by the formula (q-1) described above is exemplified, detailed description thereof is omitted here.

Further, R ¹ in the above formula (t-1), R ² and R ³ in the formula (t-2), and R ⁴ in the formula (t-3), which are respectively substituted or non-substituted Examples of the substituted arylalkyl group having 7 to 31 carbon atoms include, for example, benzyl group, phenylethyl group, 3-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 2- (1-naphthyl). ) Ethyl group, 2- (2-naphthyl) ethyl group, 3- (1-naphthyl) propyl group, 3- (2-naphthyl) propyl group and the like.

From the viewpoint of availability, R ^{1 to} R ⁴ are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, or substituted or unsubstituted aryl groups having 6 to 30 carbon atoms. It is more preferred that it is a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Further, in view of easy availability and easy handling such as viscosity, n-butyl group, n-hexyl group, 2-ethylhexyl group, dimethylphenyl group, isopropylphenyl group, and dodecylphenyl group are preferable.

S in the above formula (t-1), t and u in the formula (t-2), and v in the formula (t-3) are the number of divalent substituents-(OA ^1-4 )-. Represents an integer of 0 to 50. From the viewpoint of ease of handling due to a decrease in viscosity, etc., the above s, t, u and v are each independently preferably an integer of 1 to 40, more preferably an integer of 2 to 30. Here, when s, t, u and v are 1 or more, the ion-binding salt (1) has an oxyalkylene chain. In order to further improve the effect of the present invention, s, t, u and v are preferably 1 or more. Thus, when the ionic bond salt (1) contains an oxyalkylene chain, the oxyalkylene chain is presumed to promote the interaction between the nitrogen-containing compound and the ionic bond salt (1). Therefore, the effect of imparting slight adhesion and removability and the effect of suppressing migration are further enhanced. Therefore, s, t, u and v are more preferably 1 or more, and particularly preferably 2 or more. On the other hand, when the oxyalkylene chain is too long, the viscosity becomes high. Therefore, in consideration of handling properties, the upper limit of s, t, u and v is preferably 50, more preferably 40, and 30. And particularly preferred.

  In the ion-binding salt (1), the sulfate ester anion represented by the formula (t-1), the phosphate ester anion represented by the formula (t-2) or the sulfonate anion represented by the formula (t-3) It is appropriately selected depending on the application.

(Specific example of ion-binding salt (1))
More preferable compounds of the ion-binding salt (1) represented by the formula (1) include ion-binding salts represented by the following chemical formulas (101) to (110). Among these, from the viewpoint that the effects of the present invention can be more easily obtained, as the ion-binding salt (1), ion-binding salts represented by chemical formulas (101), (105), (107), and (109) are used. Are preferable, ion-binding salts represented by chemical formulas (101), (105), and (109) are more preferable, and ion-binding salts represented by chemical formula (101) are particularly preferable.

  The content of the ion-binding salt (1) in the slightly pressure-sensitive adhesive composition is not particularly limited, but in order to obtain the effects of the present invention sufficiently, a (meth) acrylic pressure-sensitive adhesive resin (nitrogen-containing compound and other additions) 0.1 to 20 parts by mass relative to 100 parts by mass) (excluding the agent), more preferably 0.3 to 15 parts by mass, even more preferably 0.5 to 10 parts by mass, 1-5 parts by mass is particularly preferable. If it is 0.1 mass part or more, the fine adhesiveness and re-peelability provision effect by ion binding salt (1) (and nitrogen-containing compound) can fully be acquired. On the other hand, if it is 20 parts by mass or less, the ion-binding salt (1) is not added in a large amount, so that it is not only economical, but migration can be effectively suppressed. In addition, the slightly adhesive composition according to the present invention requires only a small amount of the ion-binding salt (1) as described above, and lowers the product price compared to the case where an expensive silicone compound is added. It also has the advantage of being able to.

  In addition, an ion binding salt (1) may be used independently and may be used in mixture of 2 or more types. When using 2 or more types mixed, it is preferable in those total amount being in the said range.

(Method for producing ion-binding salt (1))
The method for producing the ion-binding salt (1) is not particularly limited as long as it can produce the ion-binding salt having the structure of the formula (1), and any method can be adopted. Can do. For example, an anion exchange method, neutralization method, acid ester method and the like can be mentioned. Further, the following deammonification method is also preferably used.

That is, an ammonium salt of a sulfate ester anion represented by the above formula (t-1) ([t-1] ⁻ [NH ₄ ] ⁺ ), an ammonium salt of a phosphate ester anion represented by the formula (t-2) ( [T-2] ^- [NH ₄ ] ⁺ ) or an ammonium salt of a sulfonate anion ([t-3] ^- [NH ₄ ] ⁺ ) represented by the formula (t-3) and the amino group or imino group By reacting the contained silane compound, the ion-binding salt (1) can be obtained. Here, as the ammonium salt of the sulfate ester, the ammonium salt of the phosphate ester, or the ammonium salt of the sulfonic acid, a commercially available product may be used, or one synthesized in advance may be used. The synthesis method is not particularly limited. For example, an ammonium salt of a sulfate ester is produced by a conventionally known method such as a method of reacting alcohols, phenols or (poly) oxyalkylene alkyl ethers with sulfamic acid. Can do.

  The reaction conditions for producing the ion-binding salt (1) are not particularly limited, but are preferably the following conditions.

  The molar ratio (preparation ratio) between the ammonium salt of sulfate ester, the ammonium salt of phosphate ester or the ammonium salt of sulfonic acid and the silane compound containing an amino group or imino group is 1: 1 to 1: 2. It is preferable that the ratio is 1: 1.2 to 1: 1.6. Within such a range, the reaction proceeds efficiently.

  The reaction solvent that can be used at the time of use is not particularly limited, and examples thereof include toluene, xylene, ethanol and the like.

  The atmosphere of the reaction is not particularly limited, and for example, the atmosphere or an inert gas atmosphere such as nitrogen or argon can be appropriately employed. From the viewpoint of preventing coloring, an inert gas atmosphere such as nitrogen or argon Preferably it is below. Under such conditions, the by-product ammonia is distilled off simultaneously with the reaction.

  The reaction proceeds simultaneously with the production of ammonia as a byproduct, and the reaction temperature is preferably 20 to 150 ° C, more preferably 50 to 130 ° C. Moreover, it is preferable that reaction time is 1 to 6 hours, and it is more preferable that it is 2 to 5 hours.

  After completion of the reaction, a solution containing the ion-binding salt (1), the unreacted raw material amino group or imino group-containing silane compound, and the reaction solvent is obtained, and the amino group or imino group-containing silane compound and reaction are obtained. The target ion-binding salt (1) is obtained by distilling off the solvent under reduced pressure. The temperature range during this vacuum distillation is preferably 40 to 170 ° C, more preferably 50 to 160 ° C. Moreover, the time of vacuum distillation is preferably in the range of 0.5 to 5 hours, more preferably in the range of 1 to 2 hours. Further, the degree of vacuum during the vacuum distillation is preferably in the range of 0.66 to 6.67 kPa (5 to 50 mmHg), more preferably in the range of 1.07 to 2.00 kPa (8 to 15 mmHg). .

[Nitrogen-containing compounds]
The nitrogen-containing compound used in the present invention may be any compound that contains at least one nitrogen atom, but considering the ease of interaction with the ion-binding salt (1), the availability, and the like. The organic compound containing at least one nitrogen atom (nitrogen-containing organic compound) is preferable.

The nitrogen-containing organic compound includes ammonia (NH ₃ ), amine compound, imidazole compound, pyridine compound, pyrrolidine compound, pyrrole compound, pyrazine compound, pyrimidine compound, triazole compound, triazine compound, quinoline compound, isoquinoline compound, indole compound, quinoxaline. It is preferably at least one selected from the group consisting of a compound, a piperazine compound, an oxazoline compound, a thiazoline compound, and a morpholine compound.

Specific examples of each of the nitrogen-containing organic compounds can include the same compounds as those described in paragraphs [0071] to [0091] of JP2012-72130A. Among the above compounds, ammonia (NH ₃ ), amine compounds and imidazole compounds are more preferable, and ammonia and amine compounds are even more preferable, from the viewpoint of easy interaction with (1) and availability. Compounds are particularly preferred.

  Among the amine compounds, dimethylamine, diethylamine, trimethylamine, monopropylamine, dipropylamine, tripropylamine, monobutylamine, dibutylamine, tributylamine, methyl (ethyl) amine, methyl (propyl) amine, methyl ( Alkylamines such as butyl) amine, methyl (pentyl) amine, methyl (hexyl) amine, ethyl (propyl) amine, ethyl (butyl) amine, ethyl (pentyl) amine, ethyl (hexyl) amine; monobenzylamine, (1 -Aromatic substituted alkyl such as phenethyl) amine, (2-phenethyl) amine (also known as monophenethylamine), dibenzylamine, bis (1-phenethyl) amine, bis (2-phenethyl) amine (also known as diphenethylamine) Cycloalkylamines such as monocyclopentylamine, dicyclopentylamine, monocyclohexylamine, dicyclohexylamine, monocycloheptylamine, dicycloheptylamine; monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, Triethanolamine, mono (n-propanol) amine, di (n-propanol) amine, tri (n-propanol) amine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine, dibutanolamine, tributanol Amine, monopentanolamine, dipentanolamine, tripentanolamine, monohexanolamine, dihexanolamine , Trihexanolamine, monomethylmonoethanolamine, monoethylmonoethanolamine (also known as N-ethylethanolamine), monoethylmonopropanolamine, monoethylmonobutanolamine, monoethylmonopentanolamine, monopropylmonoethanolamine , Monopropylmonopropanolamine, monopropylmonobutanolamine, monopropylmonopentanolamine, monobutylmonoethanolamine, monobutylmonopropanolamine, monobutylmonobutanolamine, monobutylmonopentanolamine, dimethylmonoethanolamine, Diethyl monoethanolamine (N, N-diethylethanolamine), diethyl monopropanolamine, diethyl monobutanolamine, diethyl Monopentanolamine, dipropylmonoethanolamine, dipropylmonopropanolamine, dipropylmonobutanolamine, dipropylmonopentanolamine, dibutylmonoethanolamine, dibutylmonopropanolamine, dibutylmonobutanolamine, dibutylmonopentanolamine , Monomethyldiethanolamine, monomethyldipropanolamine, monomethyldibutanolamine, monomethyldipentanolamine, monoethyldiethanolamine, monoethyldipropanolamine, monoethyldibutanolamine, monoethyldipentanolamine, monopropyldiethanolamine, monopropyldi Propanolamine, monopropyldibutanolamine, monopropyldipentanolamine, monobutyl Rudiethanolamine, monobutyldipropanolamine, monobutyldibutanolamine, monobutyldipentanolamine, monocyclohexylmonoethanolamine, monocyclohexyldiethanolamine, monocyclohexylmonopropanolamine, monocyclohexyldipropanolamine, N- (β-amino Alkanolamines such as ethyl) monoethanolamine, N-tert-butylmonoethanolamine, N-tert-butyldiethanolamine, N- (β-aminoethyl) isopropanolamine, N, N-diethylisopropanolamine are preferred. These amine compounds are preferable from the viewpoint of easy interaction with the ion-binding salt (1) and availability.

  Among the imidazole compounds, imidazole, N-isobutylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-n-propylimidazole, 2-isopropylimidazole, 2-n-butylimidazole, 2-phenylimidazole, 4 -Methylimidazole, 4-ethylimidazole, 4-nitroimidazole, 4-phenylimidazole, 2-methyl-4-phenylimidazole, 4,5-dimethylimidazole, 1-isobutyl-2-methylimidazole, 2,4,5- Imidazole compounds such as trimethylimidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-methylbenzimidazole, 2-phenylbenzimidazole are preferred. These imidazole compounds are preferable from the viewpoint of easy interaction with the ion-binding salt (1) and availability.

  Among these, alkanolamine is preferred because it can easily give the (meth) acrylic pressure-sensitive adhesive resin fine adhesion and removability by interacting with the ion-binding salt (1).

Further, the nitrogen-containing compound may be an ion-binding salt containing a cation derived from the nitrogen-containing organic compound. However, when an ion-binding salt is used as the nitrogen-containing compound, the cation contained in the nitrogen-containing compound excludes those satisfying the definition of Q ⁺ of the ion-binding salt (1).

  The cation constituting the ion-binding salt as the nitrogen-containing compound is preferably a cation derived from the nitrogen-containing organic compound described above.

On the other hand, the anion constituting the nitrogen-containing compound is not particularly limited. For example, a halide ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), an oxo acid anion (borate anion, carbonate anion, acetate anion, sulfate anion, sulfate anion, phosphate anion, phosphoric acid ester anion, sulfonic acid anion), boron-based anion (BF 4 ^_-; tetramethylborate, tetraalkylborate such tetraethyl borate rate; tetraphenylborate, tetrakis (pentafluorophenyl phenyl) tetraarylborate borate, etc.), phosphorus-based anion (PF ₆ ^-, etc.), imide anion (bis (trifluoromethanesulfonyl) imide anion of bis (perfluoroalkanesulfonyl) imide anion) and the like.

Among the above, from the viewpoint of easily obtaining the effect of the present invention, the anions constituting the nitrogen-containing compound are Cl ⁻ , Br ⁻ , sulfate anion, phosphate anion, sulfonate anion, tetraphenylborate, PF _6. ^- , Bis (trifluoromethanesulfonyl) imide anion, etc. are preferable. Further, the anion is preferably a sulfate ester anion, a phosphate ester anion, a sulfonate anion, or a bis (trifluoromethanesulfonyl) imide anion, and is represented by the formula (t-1) of the ion binding salt (1). And a sulfonate anion represented by formula (t-3) or a sulfonate anion represented by formula (t-3).

  Therefore, the nitrogen-containing compound is preferably an ion-binding salt represented by the following formula (2) (hereinafter sometimes simply referred to as “ion-binding salt (2)”):

In the above formula (2),
(Q ′) ⁺ represents ammonium ion, imidazolium ion, pyridinium ion, pyrrolidinium ion, pyrrolium ion, pyrazinium ion, pyrimidinium ion, triazolium ion, triazinium ion, quinolinium ion, isoquinolin At least one selected from the group consisting of a nium ion, an indolinium ion, a quinoxalinium ion, a piperazinium ion, an oxazolinium ion, a thiazolinium ion, and a morpholinium ion, and the above formula ( 1) It does not meet the definition of Q ⁺ in
(T ′) ⁻ is the same as the definition of T ^{− in} the above formula (1). That is, (T ′) ⁻ is a sulfate ester anion represented by the above formula (t-1), a phosphate ester anion represented by the above formula (t-2), or a sulfone represented by the above formula (t-3). It is an acid anion.

  Thus, the slightly pressure-sensitive adhesive composition according to the present invention is an ion-binding salt that is a sulfate, phosphate, or sulfonate of a cation derived from the silane compound containing the amino group or imino group. (1) and a nitrogen-containing compound (ion-binding property) that is a sulfate ester salt, phosphate ester salt, or sulfonate salt of a cation having a structure not satisfying the cation definition of the ion-binding salt (1) Salt (2)). Hereinafter, the cation and the anion constituting the ion-binding salt (2) will be described.

(Cation (Q ') ⁺ )
The (Q ′) ⁺ is a cation derived from the nitrogen-containing organic compound described above. The “ammonium ion” includes both a cation derived from ammonia (NH ₃ ) and a cation derived from an amine compound. Therefore, specific examples thereof are the same as described above, and thus detailed description thereof is omitted here. Above all, (Q ′) ⁺ is a cation derived from ammonia (NH ₃ ), an amine compound or an imidazole compound. More preferably, it is more preferably a cation derived from ammonia (NH ₃ ), an alkanolamine or an imidazole compound, and particularly preferably a cation derived from alkanolamine. Such a cation is preferable in that it promotes the interaction between the ion-binding salt (1) and the ion-binding salt (2) as the nitrogen-containing compound, and is easy to impart fine adhesion and removability. is there.

In the above, “a cation derived from ammonia (NH ₃ )”, “a cation derived from an amine compound” and “a cation derived from an imidazole compound” refer to the above-mentioned ammonia, amine compound and imidazole compound, respectively. This is positively charged with protons or carbocations added. An example of a preferred cation is an ammonium cation (NH ₄ ⁺ ); a quaternary ammonium cation such as trimethylpropylammonium; a cation derived from an alkanolamine such as monoethylmonoethanolamine or diethylmonoethanolamine; imidazole or 1-isobutyl-2 -Although the cation etc. which originate in imidazole compounds, such as methyl imidazole, are mentioned, it is not restrict | limited to these.

  Moreover, as said amine compound, the amino group contained in the said compound is primary, secondary, or tertiary from a viewpoint of the simplification of the reaction process which prepares ion binding salt (2). Further, from the viewpoint of easily obtaining the effect of the present invention, a secondary or tertiary grade is more preferred, and a secondary grade is particularly preferred.

(Anion (T ′) ⁻ )
In the formula (2), the anion ((T ′) ⁻ ) is a sulfate ester anion represented by the formula (t-1) and a phosphorus represented by the formula (t-2) according to the ion binding salt (1). Since it is the same as the acid ester anion or the sulfonate anion represented by the formula (t-3), detailed description thereof is omitted here.

The anion (T ⁻ ) of the ion-binding salt (1) and the anion ((T ′) ⁻ ) of the ion-binding salt (2) are the same in that the effects of the present invention are more easily obtained. Is preferable. When these anions are the same, the compatibility of the mutual ion-binding salt is improved, so that the ion-binding salt (1) is converted to the (meth) acrylic adhesive resin by the ion-binding salt (2). It becomes easier to fix.

(Method for producing ion-binding salt (2))
The method for producing the ion-binding salt (2) is not particularly limited as long as it can produce the ion-binding salt having the structure of the formula (2), and any method can be adopted. Can do. For example, the method for producing the ion-binding salt (1) can be appropriately modified and changed for use. More specifically, the silane compound containing an amino group or imino group used in the production of the ion-binding salt (1) may be changed to a nitrogen-containing compound constituting the cation (Q ′) ⁺ . The reaction conditions during the production of the ion-binding salt (2) are not particularly limited and are substantially the same as those of the ion-binding salt (1), and thus detailed description thereof is omitted here.

(Specific example of ion-binding salt (2) as nitrogen-containing compound)
More preferable compounds of the ion binding salt (2) represented by the chemical formula (2) include ion binding salts represented by the following chemical formulas (201) to (222). Among these, from the viewpoint that the effects of the present invention are more easily obtained, the ion-binding salt (2) is represented by chemical formulas (201), (202), (203), (204), (207), (210). , (211), (212), (217) and (222) are preferable, and the chemical formulas (201), (202), (203), (207), (210), (211) are preferable. ), (212), and ion-binding salts represented by (217) are more preferable, and ions represented by chemical formulas (201), (202), (203), (207), (212), and (217). Bonding salts are even more preferable, ion-binding salts represented by chemical formulas (201), (202), and (203) are even more preferable, and ion-binding salts represented by chemical formula (201) are particularly preferable.

  The content of the nitrogen-containing compound in the slightly pressure-sensitive adhesive composition is not particularly limited, but in order to sufficiently obtain the effects of the present invention, a (meth) acrylic pressure-sensitive adhesive resin (ion-binding salt (1) and other additions) 0.1 to 20 parts by weight, more preferably 0.15 to 20 parts by weight, even more preferably 0.3 to 15 parts by weight, with respect to 100 parts by weight) The amount is particularly preferably 0.5 to 10 parts by mass, and most preferably 1 to 5 parts by mass. If it is 0.1 mass part or more, the anchor effect by addition of a nitrogen-containing compound can fully be acquired. On the other hand, if it is 20 mass parts or less, since a nitrogen-containing compound is not added in large quantities, it is not only economical, but the physical property fall of a slightly adhesive composition can be suppressed.

  The ratio of the ion-binding salt (1) and the nitrogen-containing compound contained in the slightly pressure-sensitive adhesive composition according to the present invention is not particularly limited, but the ion-binding salt (1) and the nitrogen-containing compound are , And preferably in a mass ratio of 1: 0.1 to 1:20. Furthermore, from the reason that the effect of the present invention is more easily improved, the ratio of the ion-binding salt (1) and the nitrogen-containing compound is more preferably 1: 0.1 to 1:10, and 1: 0. 15 to 1:10 is even more preferable, 1: 0.3 to 1: 5 is particularly preferable, and 1: 1 to 1: 3 is most preferable.

  In addition, a nitrogen containing compound may be used independently and may be used in mixture of 2 or more types. When using 2 or more types mixed, it is preferable in those total amount being in the said range.

  Furthermore, in the slightly pressure-sensitive adhesive composition of the present invention, it is preferable to increase the content ratio of the nitrogen-containing compound with respect to the ion-binding salt (1). That is, it is preferable that the content of the nitrogen-containing compound with respect to the ion-binding salt (1) is equal to or more (based on mass). According to such an embodiment, the nitrogen-containing compound is taken into the (meth) acrylic adhesive resin and the ion-binding salt (1) is dispersed on the surface of the (meth) acrylic adhesive resin. It is considered that the anchor effect can be exhibited more remarkably. As a result, the ion-binding salt (1) fixed to the surface of the (meth) acrylic adhesive resin by the nitrogen-containing compound provides fine adhesion and removability and facilitates suppression of migration. In other words, simply adding only the ion-binding salt (1) does not fix the ion-binding salt (1) to the surface of the (meth) acrylic adhesive resin, and cannot contribute to the above effects. By adding a nitrogen-containing compound to disperse and fix the ion-binding salt (1) on the surface of the (meth) acrylic adhesive resin, it is greatly effective in imparting fine adhesion and removability and suppressing migration. It becomes possible to contribute. In addition, the effect of suppressing adhesion progress over time is further improved.

[Other ingredients]
In addition to the (meth) acrylic pressure-sensitive adhesive resin, the ion-binding salt (1) and the nitrogen-containing compound described above, the slightly pressure-sensitive adhesive composition according to the present invention includes a crosslinking agent, a plasticizer, and other additives as necessary. An agent or the like may be contained. Hereinafter, each of these components will be described.

(Crosslinking agent)
The cross-linking agent can adjust the properties of the pressure-sensitive adhesive such as adhesive strength, holding power, and tack by cross-linking the (meth) acrylic pressure-sensitive adhesive resin, and has a function of improving durability and heat resistance. It is an additive.

  The crosslinking agent reacts with a functional group having active hydrogen or the like (for example, a carboxyl group, a hydroxyl group, an amino group, a hydroxymethyl group, etc.) present in the (meth) acrylic adhesive resin (for example, a side chain), The adhesive resin is cross-linked, and examples thereof include isocyanates, polyvalent isocyanate compounds, polyvalent epoxy compounds, polyvalent aziridine compounds, and chelate compounds.

  Examples of the polyvalent isocyanate compound include toluylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and adduct type compounds thereof.

  Examples of the polyvalent epoxy compound include ethylene glycol diglycidyl ether, terephthalic acid diglycidyl ester acrylate, and the like.

  Examples of the polyvalent aziridine compound include tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, tris [1- (2-methyl) -aziridinyl] phosphine oxide, hexa [1- (2-methyl) -aziridinyl] triphosphatriazine and the like.

  Examples of the chelate compound include ethyl acetoacetate aluminum diisopropylate and aluminum tris (ethyl acetoacetate).

  Although the compounding quantity of a crosslinking agent can be suitably adjusted with the kind of (meth) acrylic-type adhesive resin, 0.1-40 mass parts is preferable with respect to 100 mass parts of (meth) acrylic-type adhesive resin, 1 -30 mass parts is more preferable.

(Plasticizer)
The plasticizer is an additive that can plasticize the slightly pressure-sensitive adhesive composition and contribute to improvement of wettability to the adherend.

  The kind in particular of a plasticizer is not restrict | limited, A well-known thing can be used. Examples include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), di-normal octyl phthalate (DnOP), diisononyl phthalate ( Phthalates such as DINP), dinonyl phthalate (DNP), diisodecyl phthalate (DIDP), tri-2-ethylhexyl trimellitic acid (TOTM), tri-normal octyl trimellitic acid (n-TOTM), trimellitic acid Trimellitic acid esters such as triisodecyl, adipic acid esters such as diisobutyl adipate (DIBA), dioctyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), dioctyl azelate (DOZ) Fatty acid esters such as dibutyl sebacate (DBS), dioctyl sebacate (DOS), tributyl acetyl citrate, epoxies such as epoxidized soybean oil, polyesters such as adipic acid polyester, phosphate esters such as tricresyl phosphate And citric acid esters. Among these, diisononyl adipate (DINA) is more preferable from the viewpoint of safety.

  When adding a plasticizer, the compounding quantity of a plasticizer can be suitably adjusted with the kind of (meth) acrylic-type adhesive resin, but 0.1-0.1 with respect to 100 mass parts of (meth) acrylic-type adhesive resins. 40 mass parts is preferable and 1-30 mass parts is more preferable.

(Other additives)
As other additives, conventionally known additives can be used. Specifically, for example, surface smoothing agents, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, Examples thereof include silane coupling materials, inorganic fillers, organic fillers, powders such as metal powders, colorants, and pigments, surfactants, and low molecular weight polymers. What is necessary is just to mix | blend these additives suitably according to the use application of an adhesive composition.

  The fine pressure-sensitive adhesive composition according to the present invention may contain a silicone compound as long as it is in a trace amount, but the content is preferably as small as possible in order to suppress white turbidity, phase separation, migration, and the like. Accordingly, the content of the silicone compound is preferably 5 parts by mass or less and particularly preferably 0 part by mass with respect to 100 parts by mass of the (meth) acrylic adhesive resin.

[Production Method of Slight Adhesive Composition]
The slightly pressure-sensitive adhesive composition according to the present invention can be produced, for example, by appropriately using a known organic solvent such as ethyl acetate, toluene, methyl ethyl ketone or the like, or by mixing each component with a mixer without solvent. . At this time, the method of adding each component is not particularly limited. For example, all components may be added simultaneously.

[Usage form and application of the slightly adhesive composition]
By using the slightly pressure-sensitive adhesive composition of the present invention, it is possible to form a pressure-sensitive adhesive layer that is excellent in slight pressure-sensitive adhesiveness and removability, and in which migration is suppressed. The pressure-sensitive adhesive layer is obtained by crosslinking the fine pressure-sensitive adhesive composition according to the present invention, and such a pressure-sensitive adhesive layer is also included in one aspect of the present invention.

  In addition, although the thickness of an adhesive layer is not specifically limited, Usually, it is about 1-400 micrometers, and when adhesive performance is considered, it is preferable that it is about 5-200 micrometers, and it is more preferable that it is about 10-100 micrometers.

The fine pressure-sensitive adhesive composition may be cross-linked by applying the fine pressure-sensitive adhesive composition on the adherend or release paper by a known means such as an applicator, and then heating or light irradiation. For example, heating is performed at 50 to 180 ° C. for 1 minute to 3 hours, and irradiation with ultraviolet rays having an illuminance of 1 to 200 mW / cm ² at a wavelength of 300 to 400 nm is performed by light irradiation that irradiates about 400 to 4000 mJ / cm ^2. it can.

  Applications of the slightly adhesive composition of the present invention include, for example, protective films for mobile phones, smartphones, tablet terminals and the like, protective film sheets and tapes in the electronic industry field, and temporary fixing sheets and tapes during work processes. It is done.

<Adhesive sheet>
Therefore, according to the other form of this invention, it contains the sheet-like base material and the adhesive layer formed on one surface of the said sheet-like base material, The said adhesive layer is the said fine adhesive. An adhesive sheet comprising the composition is also provided.

  The pressure-sensitive adhesive sheet is not particularly limited as long as it has a pressure-sensitive adhesive layer formed by the fine pressure-sensitive adhesive composition according to the present invention on one surface of a sheet-like base material (hereinafter also simply referred to as “base material”). Form may be sufficient. For example, the separator (release layer) may be further laminated on the pressure-sensitive adhesive layer formed on the substrate (that is, a total of three layers), or on the substrate. A form in which a strong adhesive layer is provided on the surface opposite to the side on which the adhesive layer is formed, and a separator (peeling layer) is further laminated on the strong adhesive layer (ie, a total of five layers) ). The pressure-sensitive adhesive sheet having the latter five-layer structure is, for example, a mobile phone, a smartphone, a tablet terminal or the like in a state where a separator (peeling layer) located in both outermost layers is peeled off and a protective glass is attached to a strong adhesive layer. It can be used as a double-sided adhesive tape (AB tape) as protection.

  It does not restrict | limit especially as a base material used at this time, If it is used as a base material of an adhesive sheet, it will not specifically limit. For example, a film made of a resin such as poly (meth) acrylate having a lactone ring structure or a glutarimide structure, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene, Examples thereof include a resin film obtained by mixing two or more of the above resins and a resin film obtained by laminating two or more layers. Among these, it is preferable to use PET.

  Although the thickness in particular of a base material is not restrict | limited, 10-100 micrometers is preferable, More preferably, it is 15-80 micrometers. Two or more substrates may be stacked, and in this case, the types of the substrates may be the same or different.

  Moreover, a separator (peeling layer) is not particularly limited as long as it is used as a separator for an adhesive sheet. Also about a separator, the resin film similar to the said base material is illustrated. The thickness of the separator is not particularly limited, but is preferably 10 to 100 μm, and more preferably 15 to 80 μm.

  The said adhesive sheet is not restrict | limited in particular, It can manufacture by changing a well-known method as it is or suitably. For example, a pressure-sensitive adhesive sheet is obtained by dissolving the fine pressure-sensitive adhesive composition according to the present invention in a suitable solvent to obtain a solution, and applying the solution on the substrate and drying to form a pressure-sensitive adhesive layer. Can do.

  In this case, the solvent to be used is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, propanol and isopropyl alcohol, and esters such as ethyl acetate, butyl acetate, isobutyl acetate and propyl acetate.

  Although the density | concentration of the slightly adhesive composition in a liquid mixture is not restrict | limited in particular, It is preferable that it is 30-80 mass%, and it is more preferable that it is 40-70 mass%.

  The application method is not particularly limited. For example, natural coater, knife belt coater, floating knife, roll coat, air knife coat, knife over roll, knife on blanket, reverse roll, air blade, curtain flow coater, doctor blade, wire Various coating methods using apparatuses such as a bar, a die coater, a comma coater, a spin coater, a baker applicator, and a gravure coater may be mentioned.

  The drying conditions are not particularly limited, but it is preferable to dry at a temperature at which the substrate does not deform (a temperature of about 25 to 200 ° C.) for 5 to 180 minutes.

  The thickness of the pressure-sensitive adhesive layer (thickness after drying) is not particularly limited, but a preferable thickness is as described above.

<Optical film (retardation film)>
Furthermore, the said adhesive sheet can also be used as an optical film by selecting the base material appropriately. In this case, suitable base materials include polycarbonate (PC), cycloolefin resin (COP), cellulose esters such as triacetyl cellulose (TAC) or derivatives thereof, polyester such as polyethylene terephthalate (PET), and lactone ring. Examples thereof include films made of a resin such as a (meth) acrylic resin having a structure or a glutarimide structure, and these can be used as, for example, a polarizing plate protective film. In addition, the pressure-sensitive adhesive sheet is obtained by applying a liquid crystal component to the retardation film (λ / 4 retardation film) obtained by stretching the base material and the linear polarizing film and λ / 4 retardation. It may be a circularly polarizing film (circularly polarizing plate) or the like obtained by laminating a plate. The stretched film may be a biaxially stretched film or a uniaxially stretched film.

  Although the thickness of the said base material will not be restrict | limited especially if the characteristic as an optical film can be exhibited, 10-100 micrometers is preferable, More preferably, it is 15-80 micrometers.

<Adhesion reducing agent>
As described above, by adding the ion-binding salt (1) and the nitrogen-containing compound, the adhesive composition containing the (meth) acrylic adhesive resin can be slightly adhered without using a silicone compound. Sex can be imparted.

  Therefore, according to another aspect of the present invention, the nitrogen-containing compound and the ion-binding salt (1) are added to a pressure-sensitive adhesive composition containing a (meth) acrylic pressure-sensitive adhesive resin, and Also provided is a tackiness reducing agent used to reduce the tackiness of the pressure sensitive adhesive composition.

  As described above, the ion-binding salt (1) and the nitrogen-containing compound impart slight tackiness to the pressure-sensitive adhesive composition containing the (meth) acrylic pressure-sensitive adhesive resin even if the addition amount is small. can do. Therefore, according to the tackiness reducing agent according to the present invention, the addition amount of the ion-binding salt (1) and the nitrogen-containing compound can be reduced as described above, and compared with the case of adding an expensive silicone compound, There is also an advantage that the price can be reduced.

  Specifically, the tackiness reducing agent according to the present invention is preferably added in an amount of 0.1 to 20 parts by weight, and 0.5 to 18 parts by weight added to 100 parts by weight of the (meth) acrylic adhesive resin. More preferably, it is more preferably 1 to 15 parts by mass. If it is the said range, since sufficient fine adhesiveness is provided with respect to the adhesive composition containing a (meth) acrylic-type adhesive resin, it is not necessary to add an excessive quantity, Therefore A migration can be suppressed. . Furthermore, if it is in the above-mentioned range, a sufficient effect can be obtained without excessively adding the tackiness reducing agent, which is economically advantageous.

  In addition, as described above, the tackiness reducing agent according to the present invention can impart removability to a pressure-sensitive adhesive composition containing a (meth) acrylic pressure-sensitive adhesive resin. Furthermore, the tackiness reducing agent according to the present invention can suppress adhesion progress over time.

  The usage form of the tackiness reducing agent according to the present invention is not particularly limited. For example, it may be used in a form in which a tackiness reducing agent is dispersed in a slightly pressure-sensitive adhesive composition, or may be used in a form in which a tackiness reducing agent is kneaded in a slightly pressure-sensitive adhesive composition, It may be used in a form in which a tackiness reducing agent is applied to the surface of the slightly pressure-sensitive adhesive composition, or a form in which these are appropriately combined. Any form can be used as long as at least a part of the tackiness-reducing agent can be exposed on the surface of the slightly-adhesive composition, but it is preferable to reduce tackiness in the slightly-adhesive composition. A form in which the agent is dispersed is employed. Such a form is preferable because the manufacturing process of the slightly pressure-sensitive adhesive composition is simplified.

  In the above-mentioned form, “the slightly pressure-sensitive adhesive composition contains an adhesive reducing agent” means that the constituent component (particularly, ion-binding salt (1)) contained in the adhesive reducing agent is polycondensed, Or the case where it does not remain | survive with the form at the time of addition by reacting with (meth) acrylic-type adhesive resin etc. shall also be included. That is, “the slightly pressure-sensitive adhesive composition contains an adhesion reducing agent” means that the slightly pressure-sensitive adhesive composition has a molecular structure derived from a compound constituting the adhesion reducing agent.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not restrict | limited at all by the following Example. In the following description, “part” or “%” may be used, but “part by mass” or “% by mass” is indicated unless otherwise specified.

≪Preparation of each ingredient≫
[Synthesis Example 1: Synthesis of [APM-Si] [EHDG-S]; Synthesis of ion-binding salt (1)]
150.0 parts by mass of toluene was added to 150.0 parts by mass of diethylene glycol mono-2-ethylhexyl ether (trade name: 2-ethylhexyl diglycol, abbreviation: EHDG, manufactured by Nippon Emulsifier Co., Ltd.), and the temperature was raised to 110 ° C. To this, 80.2 parts by mass of sulfamic acid was added and reacted for 3 hours. After the reaction, excess sulfamic acid was filtered off to obtain a toluene solution of diethylene glycol mono 2-ethylhexyl ether sulfate ammonium salt (abbreviation: EHDG-SF; ammonium ion is NH ₄ ⁺ ).

To 100.0 parts by mass of the 50% toluene solution of EHDG-SF obtained above, 42. 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903, abbreviation: APM-Si) is obtained. 7 parts by mass was added and reacted at 120 ° C. for 3 hours. (EHDG-SF and APM-Si molar ratio is 1: 1.5)
After completion of the reaction, toluene and unreacted APM-Si were distilled off under reduced pressure (temperature: 150 ° C., degree of vacuum: 1.33 kPa (10 mmHg)), and the desired ion-binding salt (1) (abbreviation: [APM- Si] [EHDG-S]; 72.3 parts by mass of the compound represented by the chemical formula (101) was obtained.

The NMR spectrum data of the obtained [APM-Si] [EHDG-S] are shown below.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 0.65-0.75 (t, 2H), 0.83-0.90 (m, 6H), 1.27-1.42 (m, 8H), 1.47-1.53 (m, 1H), 1.77- 1.86 (m, 2H), 2.96-3.05 (m, 2H), 3.30-3.36 (m, 2H), 3.56 (s, 11H), 3.62-3.65 (t, 2H), 3.73-3.75 (t, 2H), 4.25-4.28 (t, 2H).

[Synthesis Example 2: Synthesis of [MEM] [EHDG-S]; Synthesis of ion-binding salt (2)]
The target ionic bond is similar to Synthesis Example 1 except that N-ethylethanolamine (Nippon Emulsifier Co., Ltd., trade name: aminoalcohol MEM, abbreviation: MEM) is used instead of APM-Si. Salt (2) (abbreviation: [MEM] [EHDG-S]; compound represented by the chemical formula (201)) was obtained. At this time, the EHDG-SF and MEM molar ratio was 1: 1.5.

[Synthesis Example 3: Synthesis of [MEM] [1305-S]; Synthesis of ion-binding salt (2)]
Synthesis Example 2 except that 100.0 parts by mass of polyoxyethylene tridecyl ether sulfate ammonium salt (abbreviation: 1305-SF; ammonium ion is NH ₄ ⁺ ) was used instead of EHDG-SF. Similarly, a target ion-binding salt (2) (abbreviation: [MEM] [1305-S]; a compound represented by the above chemical formula (207)) was obtained.

[Synthesis Example 4: Synthesis of [MEM] [Cum-SO ₃ ]; Synthesis of ion-binding salt (2)]
Except for using 100.0 parts by mass of cumene sulfonic acid (o-, m-, p-cumene sulfonic acid isomer mixture) (abbreviation: Cum-SO ₃ H) instead of EHDG-SF, In the same manner as in Synthesis Example 2, the target ion-binding salt (2) (abbreviation: [MEM] [Cum-SO ₃ H]; compound represented by the chemical formula (210)) was obtained.

[Synthesis Example 5: Synthesis of [MEM] [DOSS]; Synthesis of ion-binding salt (2)]
The target ion binding property is the same as in Synthesis Example 2 except that 100.0 parts by mass of ammonium dioctylsulfosuccinate (abbreviation: DOSS-NH ₄ ) is used instead of EHDG-SF. Salt (2) (abbreviation: [MEM] [DOSS]; compound represented by the chemical formula (211)) was obtained.

[Synthesis Example 6: Synthesis of [MEM] [EHDG-P]; Synthesis of ion-binding salt (2)]
In the same manner as in Synthesis Example 2 except that 100.0 parts by mass of diethylene glycol mono 2-ethylhexyl ether phosphoric acid diester ammonium salt (abbreviation: EHDG-PNH ₄ ) was used instead of EHDG-SF, An ion-binding salt (2) (abbreviation: [MEM] [EHDG-P]; a compound represented by the above chemical formula (204)) was obtained.

[Synthesis Example 7: Synthesis of [IBM-12] [EHDG-S]; Synthesis of ion-binding salt (2)]
1-isobutyl 2-methylimidazole (manufactured by Nippon Emulsifier Co., Ltd., trade name: T-IBM-12, abbreviated name: IBM-12) was used in the same manner as in Synthesis Example 1 except that APM-Si was used. The target ion-binding salt (2) (abbreviation: [IBM-12] [EHDG-S]; compound represented by the above chemical formula (217)) was obtained.

[Synthesis Example 8: Synthesis of [APM-Si] [1305-S]; Synthesis of ion-binding salt (1)]
Except for using 100.0 parts by mass of polyoxyethylene tridecyl ether sulfate ammonium salt (abbreviation: 1305-SF; ammonium ion is NH ₄ ⁺ ) instead of EHDG-SF, Similarly, the target ion-binding salt (1) (abbreviation: [APM-Si] [1305-S]; a compound represented by the above chemical formula (105)) was obtained.

[Synthesis Example 9: Synthesis of [APM-Si] [DOSS]; Synthesis of ion-binding salt (1)]
In the same manner as in Synthesis Example 1 except that 100.0 parts by mass of ammonium dioctylsulfosuccinate (abbreviation: DOSS-NH ₄ ) was used instead of EHDG-SF, the target ion binding property was obtained. Salt (1) (abbreviation: [APM-Si] [DOSS]; compound represented by the above chemical formula (109)) was obtained.

<< Preparation of adhesive composition >>
[Example 1-1]
Acrylic adhesive resin solution (ethyl acetate solution, solid content 50% by mass, Tg of contained resin: −55 ° C.) 100 parts by mass (manufactured by Nippon Shokubai Co., Ltd., Acryset (registered trademark) AST8918E) and hexamethylene as a crosslinking agent Diisocyanate 2 parts by weight (manufactured by Asahi Kasei Chemicals Corporation, Duranate (registered trademark) D-201), 0.5 parts by weight of [APM-Si] [EHDG-S] as an ion-binding salt (1), nitrogen-containing compound [MEM] [EHDG-S] as (ion-binding salt (2)) 0.5 parts by weight are weighed into a PP cup and mixed with a spatula until uniform, and then an acrylic pressure-sensitive adhesive composition A product solution (1-1) was prepared.

[Examples 1-2 to 1-12]
In Example 1-1, except that the addition amounts of the ion-binding salt (1) and the nitrogen-containing compound (ion-binding salt (2)) were changed to the values shown in Table 1, the above In the same manner as in Example 1-1, acrylic pressure-sensitive adhesive composition solutions (1-2) to (1-12) were obtained.

[Comparative Examples 1-1 to 1-3]
Example 1-1 is the same as Example 1-1 except that the nitrogen-containing compound was not added and the amount of ion-binding salt was changed to the values shown in Table 1. Comparative acrylic pressure-sensitive adhesive composition solutions (1-1) to (1-3) were obtained.

≪Evaluation≫
An evaluation pressure-sensitive adhesive tape was prepared by the following method using the acrylic pressure-sensitive adhesive composition solutions obtained in the above Examples and Comparative Examples, and this was evaluated.

[Adhesion test (PET 180 ° peeling force (initial adhesion))]
(Reference example)
As a reference example, a 180 ° peel test was performed on a commercially available silicone resin adhesive tape in accordance with JIS Z0237: 2009. The adhesive tape comprises a PET separator (A ′: thickness 25 μm), an acrylic strong adhesive layer (B ′: thickness 10 μm), a PET base material (C ′: thickness 50 μm), a silicone resin adhesive layer ( D ′: thickness 40 μm) and a PET separator (E ′) laminated in this order.

  The PET separator (A ′) of the silicone resin adhesive tape was peeled off, and an SUS plate (F ′) was attached on the acrylic strong adhesive layer (B ′). Thereafter, the PET separator (E ′) is peeled off, and a new PET separator (G ′) (E5007, manufactured by Toyobo Co., Ltd.) is pasted on the silicone-based resin pressure-sensitive adhesive layer (D ′). After placement, the adhesive strength (gf / 25 mm) when the PET separator (G ′) was pulled in the 180 ° direction at 300 mm / min was measured. At this time, the measurement apparatus used the tester industry Co., Ltd. apparatus name: QC tensile testing machine. The results are shown in Table 1.

(Examples and Comparative Examples)
The acrylic pressure-sensitive adhesive composition solutions (1-1) to (1-12) and the comparative acrylic pressure-sensitive adhesive composition solutions (1-1) to (1-3) were used as PET substrates (C: Toyobo Co., Ltd.). Manufactured, E5000, thickness 50 μm) using an applicator so that the thickness after drying is 45 to 50 μm. Subsequently, this was heat-dried at 90 degreeC for 5 minute (s), and the adhesive layer (D: thickness 45-50 micrometers) was formed. Thereafter, a PET separator (E: manufactured by Unitika Ltd., Emblet (registered trademark) S-25, thickness 25 μm) was pasted on the pressure-sensitive adhesive layer (D), and further cured at 40 ° C. for 72 hours. Tapes (1-1) to (1-12) and comparative adhesive tapes (1-1) to (1-3) were produced.

  Next, the PET base material (C) and the SUS plate (F) of each of the adhesive tapes cut to a width of 25 mm were fixed with an acrylic strong adhesive double-sided tape (B), and allowed to stand at room temperature for 30 minutes. The adhesive strength (gf / 25 mm) when the PET separator (E) of the tape was pulled in the 180 ° direction at 300 mm / min was measured (initial adhesive strength). At this time, the same measuring instrument as that in the above reference example was used. The results are shown in Table 1.

  From the above evaluation, it was shown that the pressure-sensitive adhesive layer formed of the fine pressure-sensitive adhesive composition according to the present invention has the same fine-tackiness and removability as the silicone resin pressure-sensitive adhesive layer. On the other hand, in Comparative Example 1-2 and Comparative Example 1-3 that contain the ion-binding salt (1) but do not contain the nitrogen-containing compound, sufficient fine-tackiness and removability cannot be obtained, and (meth) acrylic The adhesive strength higher than the adhesive strength of Comparative adhesive resin (Comparative Example 1-1) was exhibited.

  Furthermore, the slightly pressure-sensitive adhesive composition according to the present invention has a slight pressure-sensitive adhesive property and removability even when the content of the ion-binding salt (1) and the nitrogen-containing compound relative to the (meth) acrylic pressure-sensitive adhesive resin is relatively small. It was also found that it can be given sufficiently. And at this time, it is shown from the result of Table 1 that the one where the mass ratio of the nitrogen-containing compound with respect to the ion-binding salt (1) is large is likely to obtain the above-mentioned effect. : Especially good results were obtained when the mass ratio of the nitrogen-containing compound was 3: 7 (Example 1-5).

[Adhesion test (change over time, vs. glass)]
(Reference example)
The commercially available silicone resin adhesive tape used in the above [Adhesion test (PET 180 ° peeling force (initial adhesion)) was evaluated in accordance with JIS Z0237: 2009. Cut the tape to a width of 25 mm, peel off the PET separator (E ′), and layer a glass plate (H ′) wiped clean with ethyl acetate on the acrylic strong adhesive layer (D ′). A reciprocating load was applied, and the pressure-sensitive adhesive layer was pressure-bonded to the glass surface, cured with a drier adjusted to 50 ° C., taken out after about 0.5 hours, 24 hours, 48 hours, 72 hours, and allowed to stand at room temperature for 30 minutes. Then, the adhesive strength (gf / 25 mm) was measured when the PET substrate was pulled at a rate of 300 mm / min in the 90 ° direction with respect to the glass. Company made the device name:. Using the QC tensile testing machine and the results are shown in Figure 1.

(Examples and Comparative Examples)
The acrylics of Examples 1-5 and 1-6 and Comparative Examples 1-2 and 1-3 are the same as those used in [Adhesion test PET 180 ° peeling force (initial adhesiveness)]. Adhesive tapes were respectively prepared using the system adhesive composition solution.

  The PET separator (E) of each adhesive tape cut to a width of 25 mm is peeled off, and a glass plate (H) wiped and cleaned with ethyl acetate is layered on the adhesive layer (D). Then, the adhesive strength (gf / 25 mm) was measured.

  The result is shown in FIG. FIG. 1 shows the change over time of the adhesive strength of the pressure-sensitive adhesive layer according to each example and comparative example. From FIG. 1, the ion-binding salt (1) and the nitrogen-containing compound (ion-binding salt (2) were compared with the adhesive tape (Comparative Examples 2 and 3) to which no nitrogen-containing compound (ion-binding salt (2)) was added. )) In combination with the adhesive tape (Examples 1-5 and 1-6), as in the case of the silicone resin adhesive tape (Reference Example), it can be seen that the initial adhesive strength to glass can be greatly reduced. Furthermore, since the adhesion progress was suppressed even after curing at 50 ° C., it was shown to exhibit the same physical properties as a commercially available silicone resin adhesive tape.

<< Preparation of adhesive composition >>
[Example 2-1]
Acrylic adhesive resin solution (ethyl acetate solution, solid content 50% by mass, Tg of contained resin: −55 ° C.) 100 parts by mass (manufactured by Nippon Shokubai Co., Ltd., Acryset (registered trademark) AST8918E), hexamethylene as a crosslinking agent 3 parts by mass of diisocyanate (manufactured by Asahi Kasei Chemicals Corporation, Duranate (registered trademark) D-201) and 10 parts by mass of diisononyl adipate (DINA) as a plasticizer (manufactured by Shin Nippon Chemical Co., Ltd., trade name Sunsosizer (registered trademark)) DINA), [APM-Si] [EHDG-S] as ion-binding salt (1) 0.5 part by mass, [MEM] [EHDG-S as nitrogen-containing compound (ion-binding salt (2)) ] Weigh 0.1 parts by weight into a PP cup and mix with a spatula until uniform. Objects solution (2-1) was prepared.

[Examples 2-2 to 2-10]
In Example 2-1 above, the acrylic compound was treated in the same manner as in Example 2-1 except that the type of nitrogen-containing compound (ion binding salt (2)) was changed as shown in Table 2-1. System pressure-sensitive adhesive composition solutions (2-2) to (2-10) were obtained.

Note that “EHDG-SF” used in Example 2-2 is diethylene glycol mono 2-ethylhexyl ether sulfate ammonium salt obtained as an intermediate in Synthesis Example 1 (abbreviation: EHDG-SF; ammonium ion is NH ₄ ⁺ A compound represented by the chemical formula (212). “[N _1,1,1,3 ] [TFSA]” in Example 2-8 is represented by trimethylpropylammonium bistrifluoromethanesulfonylimide (reagent; manufactured by Tokyo Chemical Industry Co., Ltd .; the above chemical formula (222)). Compound) is used as it is. "Amino alcohol 2A" in Example 2-9 is N, N-diethylethanolamine (manufactured by Nippon Emulsifier Co., Ltd., trade name: amino alcohol 2A, abbreviation: 2A) as it is. “T-IBM-12” in Example 2-10 uses 1-isobutyl 2-methylimidazole (manufactured by Nippon Emulsifier Co., Ltd., trade name: T-IBM-12) as it is.

[Comparative Examples 2-1 to 2-6]
In Example 2-1 above, except that the addition amounts of the ion-binding salt (1), the nitrogen-containing compound, the crosslinking agent and the plasticizer were changed as shown in Table 2-2, Example 2-1 above was changed. In the same manner as above, comparative acrylic pressure-sensitive adhesive composition solutions (2-1) to (2-6) were obtained.

[Examples 3-1 to 3-2]
In Example 2-1 above, except that the type of the ion-binding salt (1) was changed as shown in Table 3, the acrylic pressure-sensitive adhesive composition solution ( 3-1) to (3-2) were obtained.

≪Evaluation≫
An evaluation pressure-sensitive adhesive tape was prepared by the following method using the acrylic pressure-sensitive adhesive composition solutions obtained in the above Examples and Comparative Examples, and this was evaluated.

[Adhesion test (Glass 90 ° adhesion)]
(Examples and Comparative Examples)
The acrylic pressure-sensitive adhesive composition solutions (2-1) to (2-10) and (3-1) to (3-2) and the comparative acrylic pressure-sensitive adhesive composition solutions (2-1) to (2-6) ) Was applied onto a PET substrate (C: Toyobo Co., Ltd., A4300, thickness 38 μm or 50 μm) using an applicator so that the thickness after drying would be 45 to 50 μm. Subsequently, this was heat-dried at 90 degreeC for 5 minute (s), and the adhesive layer (D: thickness 45-50 micrometers) was formed. Then, on the said adhesive layer (D), PET (E: Toyobo Co., Ltd. make, E-5007, thickness 25micrometer) is affixed, Furthermore, it cures at 40 degreeC for 72 hours, Adhesive tape (2-1)- (2-10) and (3-1) to (3-2) and comparative adhesive tapes (2-1) to (2-6) were produced.

  Next, the PET (E) of each of the adhesive tapes cut to a width of 25 mm was peeled off, attached to a glass plate, and heated at 50 ° C. for 30 minutes. Thereafter, the adhesive strength (gf / 25 mm) when the PET substrate (C) was pulled in the 90 ° direction at 300 mm / min was measured. At this time, the measurement apparatus used the tester industry Co., Ltd. apparatus name: QC tensile testing machine. The results are shown in Tables 2-1 to 2-2 and Table 3 below.

[Base material adhesion]
Regarding the adhesion between the PET substrate (C) and the pressure-sensitive adhesive layer (D) when the PET substrate (C) is pulled in the 90 ° direction in the above [Adhesion test (glass 90 ° adhesive strength)] Evaluation based on the criteria of. The results are shown in Tables 2-1 to 2-2.

-Evaluation criteria-
○: Good ○ △: Only the edge is defective △: Partially defective ×: Entirely defective.

  Based on the above evaluation, the pressure-sensitive adhesive layer formed of the slightly pressure-sensitive adhesive composition according to the present invention has a small 90 ° adhesive strength, and has good slight pressure-sensitive adhesiveness and removability as compared with the comparative example. It has been shown. That is, the above result contributes to imparting good fine tack even when a compound other than [MEM] [EHDG-S] used in Example 1-1 or the like is used as the nitrogen-containing compound. It shows that you can.

  When nitrogen-containing compounds that are not ionic compounds are used (Examples 2-9 and 2-10), the 90 ° adhesive force is reduced, while the substrate adhesion is slightly reduced, and PET (E) The adhesive residue at the time of peeling (that is, a phenomenon in which a part of the pressure-sensitive adhesive layer (D) remains on the PET (E)) was confirmed. Therefore, in consideration of substrate adhesion, adhesive residue, and the like, from a practical viewpoint, the case of using a nitrogen-containing compound that is an ionic compound (Examples 2-1 to 2-8) tends to be preferable. It turned out to be. Furthermore, from the viewpoint of substrate adhesion, the anion contained in the nitrogen-containing compound used in Examples 2-1 to 2-7 (the above formula (t-1) rather than the [TFSA] anion of Example 2-8. ) To (t-3) are suggested to be preferable.

  From the above evaluation, it was shown that the pressure-sensitive adhesive layer formed by the fine pressure-sensitive adhesive composition according to the present invention has a small 90 ° adhesive strength and has good fine-tackiness and removability. That is, the above results indicate that even when a compound other than [APM-Si] [EHDG-S] used in Example 1-1 or the like is used as the ion-binding salt (1), good fine tackiness is obtained. It is shown that it can contribute to the provision of.

[Adhesion test (change over time, vs. glass)]
The acrylic adhesive composition solution (2-1) obtained in Example 2-1 was dried on a PET base material (C: manufactured by Toyobo Co., Ltd., A4300, thickness 38 μm). It apply | coated using the applicator so that it might be set to 50 micrometers. Subsequently, this was heat-dried at 90 degreeC for 5 minute (s), and the adhesive layer (D: thickness 50micrometer) was formed. Thereafter, a PET separator (E ′: manufactured by Toyo Cloth Co., Ltd., SP3000, thickness 50 μm) was bonded onto the pressure-sensitive adhesive layer (D).

  Separately from the above, DIC Corporation acrylic adhesive CT-6020 100 parts DIC Corporation FINETACK HARDENER DN: 0.4 parts, thoroughly stirred and mixed, acrylic adhesive (strong adhesive) A solution was prepared. The strong pressure-sensitive adhesive solution was applied onto a PET separator (E ': Toyo Cloth Co., Ltd., SP3000, thickness 50 µm) using an applicator so that the thickness after drying was 20 µm. Subsequently, this was heat-dried at 90 degreeC for 5 minute (s), and the acrylic strong adhesive layer (B: thickness 20 micrometers) was formed.

  Thereafter, the PET base material (C) was bonded onto the acrylic strong adhesive layer (B), and further cured at 40 ° C. for 72 hours to prepare an adhesive tape (AB tape: Sample 4-1). .

  Further, a commercially available silicone in which the thickness of the PET base material (C) is 50 μm and the pressure-sensitive adhesive layer (D) is a silicone-based resin pressure-sensitive adhesive (silicone-based resin pressure-sensitive adhesive layer (D ′: thickness 30 μm)). A resin-based resin adhesive tape was prepared as a reference example.

  The PET separator (E ′) bonded to the pressure-sensitive adhesive layer (D) or the silicone-based resin pressure-sensitive adhesive layer (D ′) of each of the pressure-sensitive adhesive tapes cut to a width of 25 mm was peeled off and attached to a glass plate. Curing is performed with a dryer adjusted to 50 ° C, and after about 0.5 hours, 24 hours, 48 hours, 72 hours, taken out and allowed to stand at room temperature for 30 minutes. The adhesive strength (gf / 25 mm) when pulled at 300 mm / min was measured. At this time, the measurement apparatus used the tester industry Co., Ltd. apparatus name: QC tensile testing machine. The results are shown in Table 4.

[Adhesion test (PET 180 ° peeling force (initial adhesion))]
Each of the adhesive tapes (Examples and Reference Examples) prepared by the method described in [Adhesion Test (Change with Time, vs. Glass)] was cut to a width of 25 mm, and a PET base material was prepared using an acrylic strong adhesive layer (B). (C) was affixed to the SUS board (F), respectively. Then, after leaving still at room temperature for 30 minutes, the adhesive force (gf / 25 mm) when the PET separator (E ′) was pulled in the 180 ° direction at 300 mm / min was measured. At this time, the measurement apparatus used the tester industry Co., Ltd. apparatus name: QC tensile testing machine. The results are shown in Table 4.

[Total light transmittance and haze evaluation]
Bonding to the pressure-sensitive adhesive layer (D) or silicone resin pressure-sensitive adhesive layer (D ′) of the pressure-sensitive adhesive tapes (Examples and Reference Examples) prepared by the method described in [Adhesion Test (Change with Time, vs. Glass)] The obtained PET separator (E ′) was peeled off and attached to a glass thin plate. Air was used as a blank, and the total light transmittance and haze were measured in a state where an adhesive tape was attached to a glass thin plate. At this time, as a measuring instrument, Nippon Denshoku Industries Co., Ltd. apparatus name: Turbidimeter (cloudiness meter) NDH2000 was used. The results are shown in Table 4.

  From the above evaluation, the pressure-sensitive adhesive tape according to the present invention not only has sufficient fine-tackiness like a silicone resin pressure-sensitive adhesive tape (reference example), but also suppresses adhesion progress even when cured at 50 ° C. ing. The pressure-sensitive adhesive tape according to the present invention also showed good values for total light transmittance and haze. Therefore, it was shown that the adhesive tape which concerns on this invention shows a physical property equivalent to a commercially available silicone resin adhesive tape.

[Optical characteristics test of optical film]
In the method described in [Adhesion test (change over time, vs. glass)], except that the PET base material (C: Toyobo Co., Ltd., A4300, thickness 38 μm) was changed to the following base material, respectively. AB tapes (Samples 4-2 and 4-3) were produced in the same manner as described above. Sample 4-1 uses a PET base material (C: manufactured by Toyobo Co., Ltd., A4300, thickness: 38 μm) as the base material.

Base material of Sample 4-2: A biaxially stretched acrylic film obtained by the method described in Example 1 of JP 2009-083307 A was used as a base material (thickness: 40 μm);
Base material of Sample 4-3: A cycloolefin polymer (COP) film obtained by the method described in Example 1 of JP-A No. 2003-114329 is used as a base material which has been stretched to a thickness of 30 μm. It was.

  Each sample obtained as described above was affixed to a liquid crystal screen, and whether or not rainbow unevenness or a blackout phenomenon occurred was confirmed through polarized sunglasses. The results are shown in Table 5.

  Based on the above evaluation, the slightly pressure-sensitive adhesive composition (and a film using the same) according to the present invention can also be applied to an optical film capable of suppressing rainbow unevenness and blackout phenomenon by appropriately selecting a substrate type. It was shown to be possible.

Claims (8)

(Meth) acrylic adhesive resin;
A nitrogen-containing compound;
A slightly pressure-sensitive adhesive composition comprising an ion-binding salt represented by the following formula (1):
In the above formula (1),
Q ⁺ is a cation derived from a silane compound containing an amino group or an imino group;
T ⁻ represents the following formula (t-1):
In the above formula (t-1),
R ¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon An aryl group having 6 to 30 atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms;
A ¹ is a linear or branched alkylene group having 2 to 4 carbon atoms,
s is an integer from 0 to 50,
Sulfate anion represented by
Following formula (t-2):
In the above formula (t-2),
R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms. A group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, wherein R ² and R ³ Is not a hydrogen atom at the same time,
A ² and A ³ are each independently a linear or branched alkylene group having 2 to 4 carbon atoms,
t and u are each independently an integer of 0 to 50;
A phosphate ester anion represented by
The following formula (t-3):
In the above formula (t-3),
R ⁴ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon An aryl group having 6 to 30 atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms;
A ⁴ is a linear or branched alkylene group having 2 to 4 carbon atoms,
v is an integer from 0 to 50,
It is a sulfonate anion shown by. In the above formula (1),
Q ⁺ represents the following formula (q-1):
In the above formula (q-1),
X is —CH ₂ — or an oxygen atom (—O—);
Y is -NH-,
Z is —N (R ⁶ ) ₂ or —N═C (R ⁶ ) ₂ ;
R ⁵ each independently represents a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. Groups, substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy groups having 3 to 20 carbon atoms, substituted or unsubstituted carbon atoms An aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (-OR ⁷ , wherein R ⁷ is a substituted or unsubstituted carbon atom; Represents 6 to 30 aryl groups),
R ⁶ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted Substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, substituted or unsubstituted 6 to 6 carbon atoms 30 aryl groups, or substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms (-OR ⁸ , wherein R ⁸ is substituted or unsubstituted carbon atoms having 6 to 30 carbon atoms. Represents an aryl group of
m is an integer of 0 to 5,
n is an integer of 0 to 5,
q is 0 or 1;
r is 0 or 1;
The slightly-adhesive composition of Claim 1 which is a cation derived from the compound shown by these. In the formula (q-1),
X is —CH ₂ —;
Z is —NH ₂ ;
At least one of R ⁵ is a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted group Or an unsubstituted aryloxy group having 6 to 30 carbon atoms,
m is an integer of 0 to 3,
n is 0;
q is 1,
The slight pressure-sensitive adhesive composition according to claim 2, wherein r is 0. The slightly pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the nitrogen-containing compound is an ion-binding salt represented by the following formula (2):
In the above formula (2),
(Q ′) ⁺ represents ammonium ion, imidazolium ion, pyridinium ion, pyrrolidinium ion, pyrrolium ion, pyrazinium ion, pyrimidinium ion, triazolium ion, triazinium ion, quinolinium ion, isoquinolin At least one selected from the group consisting of a nium ion, an indolinium ion, a quinoxalinium ion, a piperazinium ion, an oxazolinium ion, a thiazolinium ion, and a morpholinium ion, and the above formula ( 1) It does not meet the definition of Q ⁺ in
(T ′) ⁻ is the same as the definition of T ^{− in} the above formula (1).   5. The ion-bonding salt represented by the formula (1) is included in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic adhesive resin. Slight adhesive composition.   The slight adhesion according to any one of claims 1 to 5, comprising the ion-binding salt represented by the formula (1) and the nitrogen-containing compound in a mass ratio of 1: 0.1 to 1:20. Agent composition. The nitrogen-containing compound of claim 1;
An ion-binding salt represented by the formula (1) according to claim 1,
A tackiness reducing agent which is added to a pressure sensitive adhesive composition containing a (meth) acrylic pressure sensitive adhesive resin and used to reduce the tackiness of the pressure sensitive adhesive composition. A sheet-like base material, and an adhesive layer formed on one surface of the sheet-like base material,
The said adhesive layer is an adhesive sheet containing the slightly adhesive composition of any one of Claims 1-6.