JP5873292B2 - Polysilsesquioxane graft copolymer, process for producing the same, pressure-sensitive adhesive, and pressure-sensitive adhesive sheet - Google Patents

Description

  The present invention relates to a method for producing a polysilsesquioxane graft copolymer that can be an adhesive having excellent adhesiveness, heat resistance, and cohesion, a polysilsesquioxane graft copolymer, and the polysilsesquioxane graft copolymer. The present invention relates to an adhesive and an adhesive sheet using an oxan graft copolymer.

Conventionally, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed by applying a pressure-sensitive adhesive to a base sheet is known as a label sheet to be attached to various members and devices.
This pressure-sensitive adhesive sheet is widely used in many industrial fields for printing labels, packaging, and the like because of the convenience that it can be applied immediately by pressing. For example, in production management in production lines of automobiles and electric / electronic products, sticking an adhesive sheet (barcode label) printed with a barcode on a part is performed.

In production control or the like in the production line of automobiles and electric / electronic products, there are processes where heat treatment is performed depending on parts, and heat resistance is required for a label to be used.
However, although the adhesive generally used conventionally is cheap, if it processes at the temperature of about 80-150 degreeC after sticking, an adhesive will deteriorate and cohesive force will fall. As a result, there is a problem that the pressure-sensitive adhesive sheet is partially peeled due to the shrinkage of the base material and the decrease in cohesive force.

  In order to solve such a problem, Patent Document 1 discloses that a printing coat layer is provided on one surface of a base material made of a polyethylene naphthalate film, and a temperature is provided on the opposite surface of the base material. A heat-resistant label having a heat-resistant adhesive layer having an adhesive strength at 150 ° C. of 0.5 N / 25 mm or more has been proposed. Here, a rubber-based or acrylic pressure-sensitive adhesive is used as the pressure-sensitive adhesive constituting the heat-resistant pressure-sensitive adhesive layer.

Patent Document 2 describes a pressure-sensitive adhesive sheet in which a heat-sensitive pressure-sensitive adhesive layer containing a heat-resistant water-based pressure-sensitive adhesive is formed on at least one surface of a base sheet. As the heat-resistant water-based pressure-sensitive adhesive, a general water-based pressure-sensitive adhesive containing an acrylic polymer emulsion or rubber latex as a main component and a tackifying resin emulsion is used.
However, the pressure-sensitive adhesive used in the pressure-sensitive adhesive sheets described in these documents is not sufficient from the viewpoint of heat resistance and the like, and development of a new pressure-sensitive adhesive that is more excellent in heat resistance and adhesive strength. Was demanded.

  In relation to the present invention, Patent Documents 3 and 4 describe pressure-sensitive adhesives using a polysilsesquioxane graft copolymer obtained by graft polymerization of a vinyl compound.

JP 2002-275438 A JP 2003-138229 A Japanese Patent No. 4566577 WO2005 / 080459 brochure

  The present invention has been made in view of such a state of the art, and a method for producing a polysilsesquioxane graft copolymer that can be used as an adhesive having better adhesiveness, heat resistance, and cohesiveness It is an object of the present invention to provide a polysilsesquioxane graft copolymer, and a pressure-sensitive adhesive and pressure-sensitive adhesive sheet using the polysilsesquioxane graft copolymer.

  The present inventor has intensively studied to solve the above problems. As a result, a dithioester group was introduced at the end of the polysilsesquioxane compound, and this was used as a reaction starting point, and acrylamide and acrylate ester were graft-polymerized at a predetermined ratio by the MADIX method. A colorless and transparent polysilsesquioxane graft copolymer was obtained. The obtained polysilsesquioxane graft copolymer was found to be useful as a pressure-sensitive adhesive component having excellent adhesiveness, heat resistance and cohesiveness, and the present invention was completed.

  Thus, according to the present invention, the following polysilsesquioxane graft copolymers (1) to (5) and processes for producing the polysilsesquioxane graft copolymers (6) to (10): (11) The pressure-sensitive adhesive and the pressure-sensitive adhesive sheet of (12) are provided.

(1) In the molecule, the following formula (i), (ii) and / or (iii)

[Wherein, D represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a combination thereof, R ¹ represents a hydrocarbon group, and R ² represents a hydrogen atom or a carbon atom having 1 to ² carbon atoms. 18 represents an alkyl group, and R ³ represents the formula (a)

（ｒ^１は、炭素数４〜１２の炭化水素基を表す。）で表される基、及び式（ｂ）

(Wherein r ¹ represents a hydrocarbon group having 4 to 12 carbon atoms) and the formula (b)

(Wherein, r ² and r ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Moreover, even if r ² and r ³ are combined to form a ring, The ring may contain a heteroatom.), And the abundance ratio of the group represented by the formula (a) and the group represented by the formula (b) is a molar ratio. (Group represented by formula (a)) :( group represented by formula (b)) = 95: 5 to 60:40. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms, and k1, k2, and k3 are each independently Represents any natural number. ] The polysilsesquioxane graft copolymer which has a repeating unit represented by the above (except what consists only of the repeating unit represented by said Formula (i)).
(2) In the formula (b), the group represented by the formula (b) forms a ring which may contain a hetero atom by combining r ² and r ^{3 in the} formula (b). ')

The polysilsesquioxane graft copolymer according to (1), which is a group represented by the formula:
(3) The polysilsesquioxane graft copolymer according to (1) or (2), which has a number average molecular weight of 50,000 to 500,000.
(4) In the above formulas (ii) and (iii), the following formula

The repeating unit represented by the following formula (ca)

(R ² and r ¹ represent the same meaning as described above) and a block [A] composed of a repeating unit represented by the following formula (c-b):

(R ² , r ^2, and r ³ represent the same meaning as described above), and the block [A] and the block [B] are represented by the formula: − From the CH moiety side of the group represented by CH (R ⁴ ) -D-, the block array arranged so as to be-[B]-[A] or-[A]-[B]-[A] The polysilsesquioxane graft copolymer according to any one of (1) to (3), which has a polymer structure.
(5) In the above formulas (ii) and (iii), the following formula

The repeating unit represented by the following formula (ca)

(R ² and r ¹ represent the same meaning as described above) and the following formula (c-b)

(R ² , r ^2, and r ³ represent the same meaning as described above), and has a random copolymer structure consisting of a repeating unit represented by any one of (1) to (3) The polysilsesquioxane graft copolymer described in 1.
(6) In the molecule, the following formula (i), (ii-a) and / or (iii-a)

(In the formula, D represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a combination thereof, R ¹ represents a hydrocarbon group, R ⁴ represents a hydrogen atom, and 1 carbon atom. Represents an alkyl group having 6 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms in total, or an acyl group having 2 to 20 carbon atoms in total, X is an alkoxy group having 1 to 20 carbon atoms which may have a substituent, Or a polysilsesquioxane compound having a repeating unit represented by an optionally substituted aryloxy group having 6 to 20 carbon atoms (represented by the formula (i)). Excluding those consisting only of units)
Formula (1a): CH ₂ = C (R ^2a ) (R ^3a ) [wherein R ^2a represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R ^3a represents formula (a)

(Wherein r ¹ represents a hydrocarbon group having 4 to 12 carbon atoms). And the compound (1a) represented by the formula (1b): CH ₂ ═C (R ^2b ) (R ^3b ) [wherein R ^2b represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R ^3b is a group represented by the formula (b)

(R ² and r ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Further, r ² and r ³ may be combined to form a ring, The ring may contain a hetero atom.)). The compound (1b) represented by the formula (1b) is used at a molar ratio of (compound (1a)) :( compound (1b)) = 95: 5 to 60:40. Used in the graft polymerization reaction in the presence of a radical polymerization initiator,
In the molecule, formula (i), (ii) and / or (iii)

(Wherein, ^D, R 1, ^{R 2,} and .R ^{3 R 4} is representing the same meaning as above, represents the ^{R 3a} or ^{R 3b,} k1, k2 and k3 are each independently any Represents a natural number, and when k1, k2 or k3 is 2 or more, groups represented by the formula: —CH ₂ —C (R ² ) (R ³ ) — may be the same or different. .) A production method of a polysilsesquioxane graft copolymer having a repeating unit represented by formula (excluding those comprising only the repeating unit represented by formula (i)).
(7) The production method according to (6), wherein azobisisobutyronitrile is used as the radical polymerization initiator.
(8) The polysilsesquioxane compound is graft-polymerized with the compound (1b) in the presence of a radical polymerization initiator, and then the compound (1a) is graft-polymerized (6 ) Or the method for producing a polysilsesquioxane graft copolymer according to (7).
(9) In the polysilsesquioxane compound, in the presence of a radical polymerization initiator, the molar ratio of the compound (1a) to the compound (1b) is (compound (1a)) :( compound (1b)) = The polysilsesquioxane graft according to (6) or (7), wherein a mixture of the compound (1a) and the compound (1b) contained at a ratio of 95: 5 to 60:40 is graft-polymerized. A method for producing a copolymer.
(10) As a compound represented by the formula (1b), in the formula (1b), R ^2b represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R ^3b represents the formula (b), The following formula (b ′) in which r ² and r ³ are combined to form a ring that may contain a hetero atom:

(6) The manufacturing method in any one of (9) characterized by using the compound which is group represented by.
(11) The production method according to any one of (6) to (10), wherein a polysilsesquioxane graft copolymer having a number average molecular weight of 50,000 to 500,000 is produced.
(12) A pressure-sensitive adhesive comprising the polysilsesquioxane graft copolymer according to any one of (1) to (5).
(13) A pressure-sensitive adhesive sheet comprising a base material sheet and a pressure-sensitive adhesive layer formed on the base material sheet and comprising the pressure-sensitive adhesive according to (12).

Since the polysilsesquioxane graft copolymer of the present invention has excellent adhesiveness, heat resistance and cohesiveness, it is used as an adhesive component particularly in electrical / electronic product lines having a step where heat treatment is performed. It can be used suitably.
According to the method for producing a polysilsesquioxane graft copolymer of the present invention, the polysilsesquioxane graft copolymer of the present invention can be efficiently produced.
Since the pressure-sensitive adhesive and pressure-sensitive adhesive sheet of the present invention use the polysilsesquioxane graft copolymer of the present invention, they have excellent pressure-sensitive adhesiveness, heat resistance and cohesiveness.

  Hereinafter, the present invention is classified into 1) polysilsesquioxane graft copolymer, 2) method for producing polysilsesquioxane graft copolymer, 3) pressure-sensitive adhesive, and 4) pressure-sensitive adhesive sheet. Explained.

1) Polysilsesquioxane graft copolymer The polysilsesquioxane graft copolymer of the present invention is a repeating unit represented by the formula (i), (ii) and / or (iii) in the molecule. (However, the polysilsesquioxane graft polymer consisting only of the repeating unit represented by the formula (i) is excluded).

  In the formulas (ii) and (iii), D represents an alkylene group having 1 to 20 carbon atoms, an arylene group, or a combination thereof.

Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
Examples of the arylene group include o-phenylene group, m-phenylene group, p-phenylene group, 2,6-naphthylene group, 1,5-naphthylene group, 1,4′-biphenylene group, and the like.

The alkylene group and arylene group may have a substituent.
As the substituent of the alkylene group, an amino group which may have a substituent such as an amino group, a methylamino group or a dimethylamino group; a hydroxyl group; a mercapto group; an amide group, a N, N-dimethylamide group or the like An amide group which may have a group; a carboxyl group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkoxy group such as a methoxy group or an ethoxy group; an alkylthio group such as a methylthio group or an ethylthio group; And alkoxycarbonyl groups such as ethoxycarbonyl group;

Examples of the substituent for the arylene group include alkyl groups such as methyl group and ethyl group; cyano group; nitro group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups such as methoxy group and ethoxy group; And alkylthio groups such as ethylthio group; and the like.
A plurality of these substituents may be bonded to an arbitrary position of the alkylene group or arylene group in the same or different manner.

  As a combination of an alkylene group and an arylene group, at least one kind of the alkylene group which may have the substituent and at least one kind of the arylene group which may have the substituent are bonded in series. The group which consists of.

  Among these, in the present invention, since a desired graft copolymer can be easily obtained, D is preferably an alkylene group or arylene group having 1 to 6 carbon atoms, more preferably an arylene group, p- A phenylene group is particularly preferred.

In the formulas (i) and (iii), R ¹ represents a hydrocarbon group.
Examples of the hydrocarbon group for R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, and n-hexyl group. An alkyl group having 1 to 20 carbon atoms such as n-heptyl group, n-octyl group, n-nonyl group, n-decyl group; vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 3- C2-C20 alkenyl group such as butenyl group, 4-pentenyl group, 5-hexenyl group; C2-C10 alkynyl group such as ethynyl group, propargyl group, butynyl group; phenyl group, 1-naphthyl group, And aryl groups having 6 to 20 carbon atoms such as 2-naphthyl group.

The hydrocarbon group for R ¹ may have a substituent. When the hydrocarbon group for R ¹ is an alkyl group, an alkenyl group, or an alkynyl group, examples of the substituent include the same as those exemplified as the substituent for the alkylene group of D. When the hydrocarbon group for R ¹ is an aryl group, examples of the substituent include those exemplified as the substituent for the arylene group of D.
These substituents may be bonded to any position of the hydrocarbon group, and a plurality of the same or different substituents may be bonded.
Among these, in the present invention, since an intended graft copolymer can be easily obtained, R ¹ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. An aryl group of 6 to 20 is more preferable, and a phenyl group is particularly preferable.

R ² is a hydrogen atom; or methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group Represents an alkyl group having 1 to 18 carbon atoms such as n-heptyl group, n-octyl group, n-nonyl group and n-decyl group. Especially, a hydrogen atom and a C1-C6 alkyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

R ⁴ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms in total, or an acyl group having 2 to 20 carbon atoms in total. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, and n-hexyl group. Examples of the alkoxycarbonyl group having 2 to 20 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group. Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
Among these, in the present invention, since a desired graft copolymer can be easily obtained, R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom.

k1, k2, and k3 each independently represent an arbitrary natural number. When k1, k2 or k3 is 2 or more, groups represented by the formula: —CH ₂ —C (R ² ) (R ³ ) — may be the same or different.

R ³ represents a group represented by the following formula (a) or formula (b), and the ratio of the group represented by the formula (a) and the group represented by the formula (b) is a molar ratio. (Group represented by formula (a)): (Group represented by formula (b)) = 95: 5 to 60:40.

In formula (a), r ¹ represents a hydrocarbon group having 4 to 12 carbon atoms. Examples of the hydrocarbon group having 4 to 12 carbon atoms include n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, C4-C12 alkyl groups such as n-nonyl group and n-decyl group; phenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group and the like An aryl group having 6 to 12 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group and a cycloheptyl group; an aralkyl group having 7 to 12 carbon atoms such as a benzyl group and a phenethyl group; It is done.

In formula (b), r ² and r ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
Examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, n -An alkyl group having 1 to 10 carbon atoms such as a hexyl group; an aryl group such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

r ² and r ³ may be combined to form a ring as represented by the formula (b ′). The ring may contain a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and the ring may be a 5-membered ring or a 6-membered ring.
Furthermore, r ² and r ³ may each independently have a substituent such as a hydroxyl group, a cyano group, or a nitro group.
An example of a ring that may be formed by combining r ² and r ³ is shown below. In the formula, “-” represents a bond.

In the formula, Z represents CH ₂ , NCH ₃ , O, or S.
Among these, since r ² and r ³ are more suitable target compounds,

Is preferably represented by

More preferably, those having a morpholine ring, in which Z is an oxygen atom (O), are particularly preferred.
In the repeating unit represented by the above formulas (ii) and (iii), the following formula (c)

The repeating unit representing a branch polymerization site represented by the following formula (ca)

(R ² and r ¹ represent the same meaning as described above) and a block [A] composed of a repeating unit represented by the following formula (c-b):

(R ² , r ^2, and r ³ represent the same meaning as described above), and the block [A] and the block [B] are represented by the formula ( In ii) and (iii), from the CH moiety side of the group represented by the formula: -CH (R ⁴ ) -D-,-[B]-[A] or-[A]-[B]-[ A] Even if it has a block copolymer structure arranged so as to be, it is composed of the repeating unit represented by the formula (ca) and the repeating unit represented by the formula (cb). It may have a random copolymer structure.
Among these, since an adhesive component having excellent adhesive strength and cohesive strength with respect to various materials can be obtained, in the present invention, it is more preferable to have the former block copolymer structure. ] And the block [B] are represented by the formula: —CH (R ⁴ ) —D—, from the CH moiety side,-[B]-[A] or-[A]-[B]- What has the block copolymer structure arranged so that it may become [A] is more preferable.

  The number average molecular weight of the polysilsesquioxane graft copolymer of the present invention is usually 50,000 to 500,000, preferably 70,000 to 200,000. The molecular weight distribution (Mw / Mn) is usually 1.1 to 5.0, preferably 1.5 to 3.0. K1, k2 and k3 in the formulas (ii) and (iii) are not particularly limited as long as they are independently an arbitrary natural number, but are preferably set within a range satisfying the number average molecular weight.

  Although there is no restriction | limiting in particular as a manufacturing method of the polysilsesquioxane graft copolymer of this invention, It can manufacture efficiently with the manufacturing method of this invention mentioned later.

2) Production method of polysilsesquioxane graft copolymer The production method of the polysilsesquioxane graft copolymer of the present invention includes, in the molecule, the above formulas (i), (ii-a) and / or ( a polysilsesquioxane compound having a repeating unit represented by iii-a), a compound (1a) represented by the formula (1a): CH ₂ ═C (R ^2a ) (R ^3a ), and the formula (1a) 1b): a compound (1b) represented by CH ₂ ═C (R ^2b ) (R ^3b ), in a molar ratio of compound (1a) and compound (1b), (compound (1a)): (compound (1) 1b)) = 95: 5 to 60:40, and the graft polymerization reaction is carried out in the presence of a radical polymerization initiator, and the above formula (i), (ii) ) And / or (iii) It is a manufacturing method of a lysyl sesquioxane graft copolymer.

<Polysilsesquioxane compound (P)>
In the production method of the present invention, a polysilsesquioxane compound having a repeating unit represented by the formula (i), (ii-a) and / or (iii-a) in the molecule (hereinafter referred to as “polysiloxane”). Rusesquioxane compound (P) ”) is used as a starting material.
In the formulas (ii-a) and (iii-a), D, R ¹ and R ⁴ represent the same meanings as exemplified in the above item 1).

  In the above formula, X represents an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, or an amino group which may have a substituent.

Examples of the alkoxy group which may have a substituent include an alkyl group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isobutoxy group and a t-butoxy group; Group, an alkoxyalkoxy group having 2 to 10 carbon atoms such as an ethoxymethoxy group, a 1-methoxyethoxy group, and a 2-methoxyethoxy group; and the like.
Examples of the aryloxy group which may have a substituent include a phenoxy group, a 2-chlorophenoxy group, a 4-chlorophenoxy group, a 3-methylphenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. It is done.
Examples of the amino group which may have a substituent include an amino group; a mono-substituted amino group such as a methylethylamino group, a phenylamino group, and an acetylamino group; a dimethylamino group, a diethylamino group, a methylphenylamino group, and an acetylmethyl group. A disubstituted amino group such as an amino group;
Among these, X is preferably an alkoxy group from the viewpoint of reactivity.

The polysilsesquioxane compound (P) has at least (ii-a) or (iii-a) repeating units in the molecule, and only from the repeating units represented by the formula (i). Does not include.
The polysilsesquioxane compound (P) is usually (ii-a) and (iii-a), (i) and (iii-a), (ii-a) and (iii-a), or (i ), (Ii-a) and (iii-a) having a repeating unit. This copolymer may be any copolycondensate such as a random copolymer, a partial block copolymer, a complete block copolymer, and the like.

  The polysilsesquioxane compound (P) can be produced by a conventionally known method, for example, the method described in Patent Document 4. Specifically, it can be produced as follows.

(In the above formula, for the sake of convenience, the description of the repeating unit corresponding to the repeating unit represented by the formulas (i) and (ii-a) is omitted, and the repeating unit represented by the (iii-a) is used. However, the present invention is not limited to this, and q represents an arbitrary natural number.)
That is, 0 with respect to 1 part by mass of the alkoxysilane compound (4) represented by the formula (4): [Hal-CH (R ⁴ ) D] Si (OR ⁵ ) ₃ and the alkoxysilane compound (4). ˜100 times the amount of the alkoxysilane compound (5) represented by the formula (5): R ¹ Si (OR ⁶ ) ₃ is condensed in the presence of an acid catalyst or a base catalyst to form a copolycondensate (P ′ )

In the above formula, R ¹ , D, X and R ⁴ represent the same meaning as described above.
Hal represents a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.
R ⁵ and R ⁶ are each independently a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, or an isopentyl group. Represents an alkyl group having 1 to 6 carbon atoms such as a group, a neopentyl group, and an n-hexyl group.

  M represents an alkali metal atom such as lithium, sodium or potassium; an alkaline earth metal atom such as magnesium or calcium; or a transition metal atom such as iron, manganese, zinc or copper; and an alkali metal atom is preferred. n represents the valence of M.

  Specific examples of the alkoxysilane compound (4) include p-chloromethylphenyltrimethoxysilane, p-chloromethylphenyltriethoxysilane, p- (2-chloroethyl) phenyltrimethoxysilane, and p- (2-chloroethyl) phenyl. Triethoxysilane, p- (3-chloropropyl) phenyltrimethoxysilane, p- (3-chloropropyl) phenyltriethoxysilane, p-bromomethylphenyltrimethoxysilane, p-bromomethylphenyltriethoxysilane, p- (2-bromoethyl) phenyltrimethoxysilane, p- (2-bromoethyl) phenyltriethoxysilane, p- (3-bromopropyl) phenyltrimethoxysilane, p- (3-bromopropyl) phenyltriethoxysilane,

  p-chloromethylphenylmethyltrimethoxysilane, p-chloromethylphenylmethyltriethoxysilane, p- (2-chloroethyl) phenylmethyltrimethoxysilane, p- (2-chloroethyl) phenylmethyltriethoxysilane, p- (3 -Chloropropyl) phenylmethyltrimethoxysilane, p- (3-chloropropyl) phenylmethyltriethoxysilane, p-bromomethylphenylmethyltrimethoxysilane, p-bromomethylphenylmethyltriethoxysilane, p- (2-bromoethyl) ) Phenylmethyltrimethoxysilane, p- (2-bromoethyl) phenylmethyltriethoxysilane, p- (3-bromopropyl) phenylmethyltrimethoxysilane, p- (3-bromopropyl) phenylmethyltriethoxysilane 2- (p-chloromethylphenyl) ethyltrimethoxysilane, 2- (p-chloromethylphenyl) ethyltriethoxysilane, 2- (p-chloromethylphenyl) ethyltripropoxysilane, 2- (p-chloro Methylphenyl) ethyltributoxysilane, 2- (p-bromomethylphenyl) ethyltrimethoxysilane, 2- (p-bromomethylphenyl) ethyltriethoxysilane, 2- (p-bromomethylphenyl) ethyltripropoxysilane,

  2- (m-chloromethylphenyl) ethyltrimethoxysilane, 2- (m-chloromethylphenyl) ethyltriethoxysilane, 2- (m-chloromethylphenyl) ethyltripropoxysilane, 2- (m-chloromethylphenyl) ) Ethyl tributoxysilane, 2- (m-bromomethylphenyl) ethyltrimethoxysilane, 2- (m-bromomethylphenyl) ethyltriethoxysilane, 2- (m-bromomethylphenyl) ethyltripropoxysilane, 3- (P-chloromethylphenyl) propyltrimethoxysilane, 3- (p-chloromethylphenyl) propyltriethoxysilane, 3- (p-chloromethylphenyl) propyltripropoxysilane, 3- (p-chloromethylphenyl) propyl Tributoxysilane, 3- (p-Bro Methylphenyl) propyltrimethoxysilane, 3- (p-bromomethylphenyl) propyltriethoxysilane, 3- (m-bromomethylphenyl) propyltripropoxysilane, 3- (m-chloromethylphenyl) propyltrimethoxysilane, 3- (m-chloromethylphenyl) propyltriethoxysilane, 3- (m-chloromethylphenyl) propyltripropoxysilane, 3- (m-chloromethylphenyl) propyltributoxysilane, 3- (m-bromomethylphenyl) ) Propyltrimethoxysilane, 3- (m-bromomethylphenyl) propyltriethoxysilane, 3- (m-bromomethylphenyl) propyltripropoxysilane,

  4- (p-chloromethylphenyl) butyltrimethoxysilane, 4- (p-chloromethylphenyl) butyltriethoxysilane, 4- (p-chloromethylphenyl) butyltripropoxysilane, 4- (p-chloromethylphenyl) ) Butyltributoxysilane, 4- (p-bromomethylphenyl) butyltrimethoxysilane, 4- (p-bromomethylphenyl) butyltriethoxysilane, 4- (p-bromomethylphenyl) butyltripropoxysilane, 4- (P-bromomethylphenyl) phenyltrimethoxysilane, 4- (p-bromomethylphenyl) phenyltriethoxysilane, 4- (p-bromomethylphenyl) phenyltrimethoxysilane, 4- (p-bromomethylphenyl) phenyl Triethoxysilane, 4- (p-bromo Tilphenyl) phenylmethyltrimethoxysilane, 4- (p-bromomethylphenyl) phenylmethyltriethoxysilane, 4- (p-bromomethylphenyl) phenyltrimethoxysilane, 4- (p-bromomethylphenyl) phenylmethyltriethoxy Silane, 2- [4 '-(p-bromomethylphenyl) phenyl] ethyltrimethoxysilane, 2- [4'-(p-bromomethylphenyl) phenyl] ethyltriethoxysilane, 2- [4 '-(p -Bromomethylphenyl) phenyl] ethyltrimethoxysilane, 2- [4 '-(p-bromomethylphenyl) phenyl] ethyltriethoxysilane, and combinations of two or more thereof.

  Specific examples of the alkoxysilane compound (5) include (substituted) phenyltrialkoxysilanes such as phenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, phenyltriethoxysilane, and 2-methoxyphenyltriethoxysilane; methyltrimethoxy Alkyltrialkoxysilanes such as silane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane; cyanomethyltrimethoxysilane, cyanomethyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 3-cyanopropyltrimethoxysilane, 3-cyanopropyltriethoxysilane, 4-cyanobutyltrimethoxysilane Cyanoalkyltrialkoxysilanes such as 4-cyanobutyltriethoxysilane; acetoxy groups such as acetoxymethyltrimethoxysilane, acetoxymethyltriethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-acetoxypropyltriethoxysilane And the combination of these two or more.

  Although the ratio of the alkoxysilane compound (4) and the alkoxysilane compound (5) constituting the copolycondensate (P ′) can be arbitrarily set, usually the alkoxysilane compound (4) is in mass parts ratio. : Alkoxysilane compound (5) = 100: 0 to 1:99.

  Examples of the acid catalyst used include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic materials such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, sulfonic acid, methanesulfonic acid, ethanesulfonic acid, acetic acid, and formic acid. Examples include acids.

  As the base catalyst, metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, potassium t-butoxide, magnesium methoxide, magnesium Metal alkoxides such as ethoxide; primary amines such as methylamine, ethylamine and butylamine; secondary amines such as diethylamine and dibutylamine; tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 1,8-diazabicyclo [5.4 0.0] nitrogen-containing heterocyclic compounds such as undec-7-ene (DBU);

  The usage-amount of an acid catalyst or a base catalyst is 0.001 weight%-10 weight% normally with respect to an alkoxysilane compound (4), Preferably it is the range of 0.01 weight%-5 weight%.

  Examples of the organic solvent used in the reaction between the alkoxysilane compound (4) and the alkoxysilane compound (5) include aromatic hydrocarbons such as benzene, toluene, and xylene; methyl acetate, ethyl acetate, propyl acetate, and methyl propionate. Esters such as acetone; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol Alcohols such as; water; and the like. These solvents can be used alone or in combination of two or more.

  The reaction temperature is usually in the temperature range from 0 ° C. to the boiling point of the solvent used, preferably in the range of 40 ° C. to 130 ° C. When the reaction temperature is too low, the progress of the condensation reaction may be insufficient. On the other hand, when the reaction temperature is too high, it is difficult to suppress gelation. The reaction is usually completed within minutes to hours.

Next, a polysilsesquioxane compound is obtained by reacting the obtained copolycondensate (P ′) with a compound (6) represented by the formula (6): M [SC (═S) X] _n . (P) can be obtained. That is, by reacting the obtained copolycondensate (P ′) with the compound (6), the halogen moiety derived from the alkoxysilane compound (4) is represented by the formula: —SC (═S) —X. The polysilsesquioxane compound (P) substituted with the group to be obtained is obtained.

Specific examples of the compound (6) include compounds in which X is an alkoxy group such as potassium ethyl xanthate and sodium ethyl xanthate;
Compounds wherein X is an aryloxy group, such as potassium phenoxyxanthate, sodium phenoxyxanthate;
Among these, since the reactivity is high and the resulting polysilsesquioxane compound can efficiently synthesize a polysilsesquioxane graft copolymer, in formula (6), X is an alkoxy group. Are preferred, ethyl xanthate is more preferred, and potassium ethyl xanthate is particularly preferred.

The reaction between the copolycondensate (P ′) and the compound (6) can be usually performed in an inert solvent.
Solvents used include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane, cycloheptane and cyclo Alicyclic hydrocarbons such as octane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, carbon tetrachloride, 1, Halogenated hydrocarbons such as 2-dichloroethane and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone Ketones; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethyl sulfoxide and sulfolane; It is done. These solvents can be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the usage-amount of a solvent, It is 1-1000 ml normally with respect to 1 g of copolycondensates (P ') to be used, Preferably it is 5-100 ml.

The reaction temperature is not particularly limited, but is usually a temperature range from 0 ° C. to the boiling point of the solvent used, preferably 15 to 60 ° C., more preferably room temperature.
The reaction time is usually several minutes to several tens of hours, preferably 1 to 20 hours.
The polysilsesquioxane compound (P) used for this invention can be obtained by performing normal post-processing operation after completion | finish of reaction.
The polysilsesquioxane compound (P) may have a ladder structure, but whether or not it has a ladder structure can be determined by, for example, performing an infrared absorption spectrum or X-ray diffraction measurement of the reaction product. Can be confirmed.

  The number average molecular weight of the polysilsesquioxane compound (P) is usually in the range of 1,000 to 30,000, preferably 1,500 to 20,000. The molecular weight distribution (Mw / Mn) of the polysilsesquioxane compound (P) is not particularly limited, but is usually 1.0 to 3.0, preferably 1.1 to 2.0. The number average molecular weight and molecular weight distribution can be measured by, for example, SEC (size exclusion chromatography) and calculated by polystyrene conversion.

Next, the resulting polysilsesquioxane compound (P) is added to the compound (1a) represented by the formula (1a): CH ₂ ═C (R ^2a ) (R ^3a ) and the formula (1b): CH ₂ = C (R ^2b ) (R ^3b ) is represented by a compound (1a) :( compound (1b)) = the compound (1a) and the compound (1b) in a molar ratio. Using the ratio of 95: 5 to 60:40 in the presence of a radical polymerization initiator, the graft polymerization reaction (that is, the reaction by the MADIX method) is carried out to obtain the desired polysilsesquioxane graft copolymer Coalescence can be obtained.

<Compound (1a)>
The compound (1a) used in the present invention is a compound represented by the formula (1a): CH ₂ ═C (R ^2a ) (R ^3a ).
In formula (1a), R ^2a represents the same meaning as R ² described above, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group.
R ^3a represents a group represented by the formula (a), wherein r ¹ represents the same meaning as described above.

Examples of the compound (1a) include the following compounds.
n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) C 4-12 alkyl esters of (meth) acrylic acid such as acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate;
C 5-12 cycloalkyl esters of (meth) acrylic acid such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate;
Aralkyl esters of carbon 7-12 of (meth) acrylic acid such as benzyl (meth) acrylate, phenacyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate;
;
Aryl esters of carbon 6-12 of (meth) acrylic acid such as phenyl (meth) acrylate, naphthyl (meth) acrylate;
Here, “(meth) acrylate” means “acrylate” or “methacrylate”, and “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid” (the same applies hereinafter). .)
A compound (1a) can be used individually by 1 type or in combination of 2 or more types.

  Among these, as a compound (1a), C4-C12 alkyl (meth) acrylates, such as n-butyl (meth) acrylate, from a viewpoint which can obtain the target polysilsesquioxane compound more easily. preferable.

<Compound (1b)>
The compound (1b) used in the present invention is a compound represented by the formula (1b): CH ₂ ═C (R ^2b ) (R ^3b ).
In formula (1b), R ^2b represents the same meaning as R ² above, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group.
R ^3b represents a group represented by the formula (b), in which r ² and r ³ have the same meaning as described above.

Examples of the compound (1b) include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, and N- (meta). ) Acryloylmorpholine, N- (meth) acryloylthiomorpholine, N- (meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine and the like.
Here, “(meth) acryloyl” means “acryloyl” or “methacryloyl” [the same applies hereinafter. ].
A compound (1b) can be used individually by 1 type or in combination of 2 or more types.

Among these, as the compound (1b), r ² and r ³ such as N- (meth) acryloylmorpholine are combined to form a ring from the viewpoint of easily obtaining the desired polysilsesquioxane compound. Is preferred, (meth) acryloylmorpholine represented by the following formula is more preferred, and acryloylmorpholine is particularly preferred.

<Reaction by MIXIX method>
In the present invention, the polysilsesquioxane compound (P), the compound (1a) and the compound (1b) are subjected to a graft polymerization reaction in the presence of a radical polymerization initiator, to thereby obtain a target polysil A sesquioxane graft copolymer can be obtained.
More specifically, the desired polysilsesquioxane graft copolymer can be obtained from the polysilsesquioxane compound (P), the compound (1a), and the compound (1b) by the MADIX method. .

Here, the MADIX method is a reversible addition-fragmentation chain transfer polymerization method (Macromolecular Design via Interchange of Xanthate) using a transfer active xanthate. That is, xanthate is used as a dormant species (a stable chemical species that is also called a dormant species in a radical reaction), and a radical species is generated by a reversible addition-cleavage reaction between this and the radical species.
In the present invention, the compound (1b) can also be efficiently graft-polymerized by using the MADIX method, so that the desired product can be easily obtained.

  Specifically, the reaction is carried out by stirring the polysilsesquioxane compound (P), the compound (1a) and the compound (1b) in a solvent in the presence of a radical polymerization initiator. The reaction is preferably performed in an inert atmosphere such as a nitrogen atmosphere.

  In the present invention, the compound (1a) and the compound (1b) are mixed in a molar ratio of the compound (1a) and the compound (1b) (compound (1a)) :( compound (1b)) = 95: 5-60 : Used at a ratio of 40. As a result, a polysilsesquioxane graft copolymer useful as an adhesive component excellent in adhesiveness, heat resistance and cohesiveness can be obtained by using at such a ratio.

  Moreover, the use ratio of the polysilsesquioxane compound (P) and the compound (total of the compound (1a) and the compound (1b)) is a molar ratio of the polysilsesquioxane compound (P) and the compound. Usually, (polysilsesquioxane compound (P)) :( compound) = 1: 20 to 1: 100, preferably 1:40 to 1:80.

Examples of the radical polymerization initiator used include azobisisobutyronitrile (AIBN), 2,2′-azobis (2-aminodipropane) dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), and the like. And azo initiators; peroxide radical polymerization initiators such as benzoyl peroxide; and the like. Among these, AIBN is preferable because the target product can be obtained efficiently.
The usage-amount of a radical polymerization initiator is 0.01-0.3 equivalent normally with respect to 1 equivalent of polysilsesquioxane compounds (P).

  The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran (THF), dioxane, anisole, phenylethyl ether, diphenyl ether; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and cyclooctane; chloroform, carbon tetrachloride, 1, Halogenated hydrocarbons such as 2-dichloroethane and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like Ketones; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethyl sulfoxide and sulfolane; . These solvents can be used alone or in combination of two or more.

  The amount of the solvent used is usually 0.1 to 1,000 ml, preferably 1 to 100 ml, per 1 g of the polysilsesquioxane compound (P).

The reaction temperature is usually in the temperature range from 20 ° C. to the boiling point of the solvent used, preferably 40-100 ° C.
The reaction time is usually several minutes to several tens of hours, preferably 1 to 10 hours, depending on the reaction scale.

  In this reaction, a mixture of compound (1a) and compound (1b) is reacted with polysilsesquioxane compound (P), and the graft chain is a random copolymer of compound (1a) and compound (1b). The compound (1a) and the compound (1b) may be added stepwise so that the graft chain becomes a block copolymer of the compound (1a) and the compound (1b). You may react so that it may become.

When compound (1a) and compound (1b) are added stepwise, it is preferable to react compound (1a) after reacting compound (1b).
By reacting in this way, the end of the graft chain is changed to the block [A] composed of the repeating unit derived from the compound (1a), so that the polysilsesquioxane graft copolymer having excellent adhesion to various materials can be used. A polymer can be obtained.

  The block copolymer of graft chains is not limited to a diblock body but may be a triblock body or a multiblock body. Even in these cases, for the same reason as described above, the terminal block of the graft chain is preferably a block [A] composed of a repeating unit derived from the compound (1a).

  In the case of performing the reaction stepwise, the reaction temperature and reaction time may be selected within the range of the reaction temperature and reaction time described above.

  After completion of the reaction, according to a well-known method, the remaining monomer and / or solvent is distilled off, and reprecipitation is performed in an appropriate solvent. The precipitated polymer is recovered by a conventionally known method to obtain a single target polymer. Can be separated.

  Solvents used for reprecipitation include water; hydrocarbons or alicyclic hydrocarbons having 5 to 8 carbon atoms such as n-pentane, n-hexane, n-heptane, cyclohexane; methanol, ethanol, isopropanol, etc. Examples thereof include alcohols having 1 to 6 carbon atoms; ethers such as diethyl ether and dioxane; Among these, n-hexane, methanol, water, diethyl ether, or a mixed solvent thereof is preferable.

As described above, a polysilsesquioxane graft copolymer having a repeating unit represented by the formula (i), (ii) and / or (iii) (the repeating unit represented by the formula (i)) Except those consisting only of).
In the formulas (i), (ii), and (iii), D, R ¹ , R ² , R ³ , R ⁴ , k1, k2, and k3 represent the same meaning as described above.

The number average molecular weight of the resulting polysilsesquioxane graft copolymer is 50,000 to 500,000, preferably 70,000 to 200,000. K1, k2 and k3 in the formulas (ii) and (iii) are not particularly limited as long as they are independently an arbitrary natural number, but are preferably set within a range satisfying the number average molecular weight.
Since this thing is excellent in adhesiveness, heat resistance, and aggregability, it can be used suitably as an adhesive.

3) Adhesive The adhesive of the present invention is characterized by containing the polysilsesquioxane graft copolymer of the present invention.
The pressure-sensitive adhesive of the present invention may be produced by dissolving one or more of the polysilsesquioxane graft copolymers of the present invention in a suitable solvent.

The solvent to be used is not particularly limited as long as it dissolves the polysilsesquioxane graft copolymer of the present invention.
For example, esters such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone; N, N-dimethylformamide, N, N-dimethylaceta Amides such as amide, N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethyl sulfoxide and sulfolane; aromatic hydrocarbons such as benzene, toluene and xylene; n-pentane, n-hexane, aliphatic hydrocarbons such as n-heptane and n-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and cyclooctane; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, Tetrahydrofuran, dioxane and the like; chloroform, carbon tetrachloride, 1,2-dichloroethane, halogenated hydrocarbons such as chlorobenzene; and the like. These solvents can be used alone or in combination of two or more.

  Although the usage-amount of a solvent is arbitrary, it is 1-10,000 mass parts normally with respect to 100 mass parts of polysilsesquioxane graft copolymers of this invention, Preferably it is 10-1,000 mass parts. .

  The pressure-sensitive adhesive of the present invention contains the polysilsesquioxane graft copolymer of the present invention as a main component, and, if desired, other pressure-sensitive adhesives, tackifiers, antioxidants, ultraviolet absorbers, light stabilizers, Softeners, fillers and the like can be added.

  Since the pressure-sensitive adhesive of the present invention contains the polysilsesquioxane graft copolymer of the present invention as a main component, it is excellent in adhesiveness and heat resistance and has cohesiveness.

4) Adhesive sheet The adhesive sheet of this invention has a base material sheet and the adhesive layer which consists of an adhesive of this invention formed on this base material sheet, It is characterized by the above-mentioned.
As the base sheet to be used, paper base materials such as glassine paper, coated paper and cast paper; polyester films such as polyethylene terephthalate film, polybutylene terephthalate film and polyethylene naphthalate film; polyolefin films such as polypropylene film and polyethylene film; Polyvinyl chloride film; Polyurethane film; Polyimide; Polyetherimide film; Synthetic paper, cellulosic sheet or film, non-woven fabric, woven fabric, knitted fabric made of various materials; metal foil; Moreover, these base material sheets can also carry out printing of an appropriate character, a pattern, etc. on the surface if desired.

  As a method of forming the pressure-sensitive adhesive layer on the base sheet, (i) a method of applying the pressure-sensitive adhesive of the present invention on the base sheet so as to have a predetermined thickness and drying at 40 to 150 ° C., (Ii) On the release sheet (or process paper), the pressure-sensitive adhesive of the present invention is applied so as to have a predetermined thickness, and the substrate sheet is bonded to the coated surface and dried at 40 to 150 ° C., It can manufacture by the method of peeling a peeling sheet, etc. In the case of the method (ii), the release sheet may be attached as it is without being peeled off if desired, and may be peeled off when the pressure-sensitive adhesive sheet is used.

  Examples of release sheets used include: paper base materials such as glassine paper, coated paper, cast paper; polyester films such as polyethylene terephthalate film, polybutylene terephthalate film and polyethylene naphthalate film; polyolefin films such as polypropylene film and polyethylene film; Can be mentioned. These release sheets may be obtained by applying a release agent such as a silicone resin, a fluorine resin, a long-chain alkyl group-containing carbamate resin, or an alkyd resin to the surface facing the pressure-sensitive adhesive layer.

  The method for coating the pressure-sensitive adhesive on the base sheet or release sheet is not particularly limited, and a known coating method can be employed. Examples of the coating method include reverse coating, gravure coating, reverse gravure, kiss coating, knife coating, bar coating, die coating, and curtain coating. The thickness of the obtained pressure-sensitive adhesive layer is usually 5 to 100 μm, preferably 10 to 60 μm.

The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive of the present invention that is excellent in adhesiveness, heat resistance, and cohesiveness. However, the cohesive force (holding force) does not decrease.
The pressure-sensitive adhesive sheet of the present invention includes not only various adherends such as a metal plate such as SUS; a resin plate such as polymethacrylate (PMMA); a glass plate such as soda lime glass; Exhibits excellent adhesion and cohesion on the body.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.

  The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymer were measured by size exclusion chromatography (SEC) using tetrahydrofuran (THF) as a developing solvent, and were converted into standard polystyrene equivalent values. Asked.

(Production Example 1) Synthesis of polysilsesquioxane compound (P)

(In the above formula, for convenience, the description of the repeating unit corresponding to the repeating unit represented by the formula (i) is omitted, and the repeating unit represented by the formula (ii-a) and the formula (iii-a)) (The equivalent is described in the state where the upper and lower sides are combined alternately in the formula, where n represents an arbitrary natural number.)

<Synthesis of copolycondensate (P ')>
In a 200 mL eggplant flask, 15 mL of a toluene / water mixed solution (volume ratio = 2/1), 4.94 g (0.02 mol) of p-chloromethylphenyltrimethoxysilane (manufactured by AMAX Co.), phenyltrimethoxysilane (Tokyo) 3.97 g (0.02 mol) manufactured by Kasei Kogyo Co., Ltd. and 0.19 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged and stirred at room temperature (25 ° C.) for 16 hours. After completion of the reaction, the organic layer was separated from the reaction solution, the solvent was distilled off under reduced pressure, and the resulting residue was added dropwise to a large amount of n-hexane. The precipitated solid was filtered off, dried, and the copolycondensate (P ′), which is a copolycondensate (P ′) as a precursor, and a copolycondensate of phenyltrimethoxysilane (hereinafter referred to as “BzClPSQ”). (Yield: 83%). The obtained BzClPSQ had a number average molecular weight (Mn) of 2,300 and a molecular weight distribution (Mw / Mn) of 1.52.

IR spectrum data of the obtained BzClPSQ is shown below.
Si—Ph: 698 cm ⁻¹ , 737 cm ⁻¹ , Si—O—Si: 1129 cm ⁻¹

<Synthesis of Polysilsesquioxane Compound (P-1)>
A 200 mL eggplant flask was charged with 50 mL of acetone and 5.58 g of the obtained BzClPSQ, and while maintaining at 0 ° C., a solution of 3.53 g (22 mol) of ethyl xanthate (Tokyo Chemical Industry Co., Ltd.) in 30 mL of acetone (30 mL) It was added dropwise over a period of minutes. Then, it stirred at room temperature (25 degreeC) for 16 hours. After completion of the reaction, the precipitate in the reaction solution was filtered by suction filtration, and the filtrate was added dropwise to a large amount of methanol / water mixed solution (volume ratio = 3/1). The precipitated solid was collected by filtration and dried to obtain the desired polysilsesquioxane compound (P) xanthate compound (hereinafter sometimes abbreviated as “XaPSQ”) (yield: 95%). The number average molecular weight (Mn) of the obtained XaPSQ was 2,800, and the molecular weight distribution (Mw / Mn) was 1.66.

IR spectrum data of the obtained XaPSQ is shown below.
Si—Ph: 699 cm ⁻¹ , 734 cm ⁻¹ , Si—O—Si: 1130 cm ⁻¹ , C—S: 1221 cm ⁻¹

Example 1 Synthesis of Polysilsesquioxane Graft Copolymer 1 XaPSQ, AIBN, butyl acrylate (BA) and acryloylmorpholine (ACMO) obtained in Production Example 1 were placed in a 100 mL two-necked eggplant flask under a nitrogen atmosphere. Was added at a molar ratio shown in Table 1 (the molar ratio of XaPSQ in Table 1 is based on a dithioester group. The same applies hereinafter). Further, an anisole was added in an amount to a concentration of 1.7 mol / L, and the whole volume was stirred at the reaction temperature shown in Table 1 for a predetermined time. After completion of the reaction, the reaction solution was added dropwise to a large amount of n-hexane or methanol, and the precipitate was collected and dried to obtain polysilsesquioxane graft copolymer 1. Table 1 shows the yield (%), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the resulting polysilsesquioxane graft copolymer 1. In Table 1, the polysilsesquioxane graft copolymer, the polysilsesquioxane graft polymer, and the copolymer are collectively referred to as “polymer”.

IR spectrum data of the resulting polysilsesquioxane graft polymer are shown below.
Si—O—Si, C—O—C: 1163 cm ⁻¹ , C═O (amide bond): 1645 cm ⁻¹ , C═O (ester bond): 1732 cm ⁻¹ , —CH ₂ −: 2874 cm ⁻¹ , 2960 cm ^-1

Example 2 Synthesis of Polysilsesquioxane Graft Copolymer 2 XaPSQ, AIBN and BA obtained in Production Example 1 were added to a 100 mL 2-neck eggplant flask in a nitrogen atmosphere at a molar ratio shown in Table 1 below. did. Further, an anisole was added in an amount to a concentration of 1.7 mol / L, and the whole volume was stirred at the reaction temperature shown in Table 1 for a predetermined time. Next, ACMO was added at a molar ratio shown in Table 1, and the whole volume was stirred at the reaction temperature shown in Table 1 for a predetermined time. After completion of the reaction, the reaction solution was added dropwise to a large amount of methanol, and the precipitate was collected and dried to obtain polysilsesquioxane graft copolymer 2. The reaction yield (%), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the resulting polysilsesquioxane graft copolymer 2 are shown in Table 1 below.

IR spectrum data of the resulting polysilsesquioxane graft copolymer 2 are shown below.
Si—O—Si, C—O—C: 1163 cm ⁻¹ , C═O (amide bond): 1644 cm ⁻¹ , C═O (ester bond): 1733 cm ⁻¹ , —CH ₂ —: 2874 cm ⁻¹ , 2960 cm ^-1

Examples 3 to 5 Synthesis of Polysilsesquioxane Graft Copolymers 3 to 5 Table 1 below shows XaPSQ, AIBN, and ACMO obtained in Production Example 1 in a 100 mL two-necked eggplant flask under a nitrogen atmosphere. Added in molar ratio. Further, an anisole was added in an amount to a concentration of 1.7 mol / L, and the whole volume was stirred at the reaction temperature shown in Table 1 for a predetermined time. Next, BA was added at a molar ratio shown in Table 1, and the whole volume was stirred at the reaction temperature shown in Table 1 for a predetermined time. After completion of the reaction, the reaction solution was added dropwise to a large amount of methanol, and the precipitate was collected and dried to obtain polysilsesquioxane graft copolymers 3 to 5. Table 1 shows the reaction yield (%), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the obtained polysilsesquioxane graft copolymers 3 to 5.

IR spectrum data of the obtained polysilsesquioxane graft copolymer 3 are shown below.
Si—O—Si, C—O—C: 1164 cm ⁻¹ , C═O (amide bond): 1641 cm ⁻¹ , C═O (ester bond): 1737 cm ⁻¹ , —CH ₂ —: 2874 cm ⁻¹ , 2960 cm ^-1

IR spectrum data of the obtained polysilsesquioxane graft copolymer 4 are shown below.
Si—O—Si, C—O—C: 1164 cm ⁻¹ , C═O (amide bond): 1640 cm ⁻¹ , C═O (ester bond): 1737 cm ⁻¹ , —CH ₂ −: 2874 cm ⁻¹ , 2960 cm ^-1

IR spectrum data of the obtained polysilsesquioxane graft copolymer 5 are shown below.
Si—O—Si, C—O—C: 1163 cm ⁻¹ , C═O (amide bond): 1640 cm ⁻¹ , C═O (ester bond): 1734 cm ⁻¹ , —CH ₂ −: 2875 cm ⁻¹ , 2960 cm ^-1

(Comparative Example 1) Synthesis of Polysilsesquioxane Graft Polymer 1r A polysilsesquioxane graft polymer 1r was prepared in the same manner as in Example 1 except that ACMO was not used and BA was used at a molar ratio shown in Table 1. Rusesquioxane graft polymer 1r was obtained. Table 1 shows the yield (%), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the resulting polysilsesquioxane graft polymer 1r.

IR spectrum data of the obtained polysilsesquioxane graft polymer 1r are shown below.
Si—O—Si, C—O—C: 1163 cm ⁻¹ , C═O (ester bond): 1733 cm ⁻¹ , —CH ₂ —: 2874 cm ⁻¹ , 2960 cm ⁻¹

(Comparative example 2) Production of copolymer 2r of BA and ACMO by free radical polymerization In a 1000 mL separable flask, 0.2 g of AIBN, 83.3 g of BA, 16.7 g of ACMO, 230 g of ethyl acetate, and 20 g of toluene were added. The mixture was stirred and stirred at 60 ° C. for 16 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was added dropwise to a large amount of methanol, and the precipitate was collected and dried to obtain a copolymer 2r. Table 1 shows the reaction yield (%), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the obtained copolymer 2r.

IR spectrum data of the obtained copolymer 2r are shown below.
C—O—C: 1164 cm ⁻¹ , C═O (amide bond): 1646 cm ⁻¹ , C═O (ester bond): 1733 cm ⁻¹ , —CH ₂ —: 2874 cm ⁻¹ , 2960 cm ⁻¹

Comparative Example 3 Synthesis of Polysilsesquioxane Graft Copolymer 3r Polysilsesquioxane was prepared in the same manner as in Example 3 except that ACMO and BA were used in the molar ratio shown in Table 1 below. Oxan graft copolymer 3r was obtained. Table 1 shows the reaction yield (%), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the resulting polysilsesquioxane graft polymer 3r.

IR spectrum data of the obtained polysilsesquioxane graft copolymer 3r are shown below.
Si—O—Si, C—O—C: 1164 cm ⁻¹ , C═O (amide bond): 1646 cm ⁻¹ , C═O (ester bond): 1734 cm ⁻¹ , —CH ₂ −: 2875 cm ⁻¹ , 2960 cm ^-1

(Comparative Example 4) Synthesis of Polysilsesquioxane Graft Copolymer 4r In Example 2, methyl methacrylate (MMA) was used instead of ACMO, and the molar ratio, reaction temperature, and reaction time shown in Table 1 were used. A polysilsesquioxane graft copolymer 4r was obtained in the same manner as in Example 2 except that the reaction was performed. Table 1 shows the yield (%), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the resulting polysilsesquioxane graft copolymer 4r.

IR spectrum data of the resulting polysilsesquioxane graft copolymer 4r are shown below.
Si—O—Si, C—O—C: 1163 cm ⁻¹ , C═O (ester bond): 1733 cm ⁻¹ , —CH ₂ —: 2875 cm ⁻¹ , 2959 cm ⁻¹

(Examples 6-10, Comparative Examples 5-8) Preparation of pressure-sensitive adhesives 1-5, 1r-4r For the polymers 1-5, 1r-4r obtained in Examples 1-5 and Comparative Examples 1-4 Then, pressure-sensitive adhesives 1 to 5 and 1r to 4r were respectively prepared by adding ethyl acetate to a concentration of 30% and mixing well.

(Examples 11 to 15 and Comparative Examples 9 to 12) Preparation of Adhesive Sheets 1 to 5, 1r to 4r Adhesives 1 to 5 and 1r to 4r obtained in Examples 6 to 10 and Comparative Examples 5 to 8 were used as base materials. As above, it was applied to one side of a transparent polyethylene terephthalate film (PET film) having a thickness of 50 μm so that the thickness after drying was 20 μm and heated at 100 ° C. for 1 minute to form an adhesive layer. Next, by attaching a release sheet (product name “SP-PET381031”, thickness 38 μm, PET film surface-treated with a silicone release agent) to the surface of the adhesive layer, adhesive sheets 1 to 5 1r to 4r were prepared.

(Adhesion test)
The obtained pressure-sensitive adhesive sheets 1 to 5, 1r to 4r were cut into a size of 25 mm × 300 mm, and the release sheet was peeled off in an environment of 23 ° C. and 50% RH (relative humidity) and attached to the following adherend. . At the time of sticking, a roller having a weight of 2 kg was used to reciprocate once and pressure-bond to the adherend. Then, after being left for 24 hours after being attached in an environment of 23 ° C. and 50% RH, a peeling speed of 300 mm / min was used in the same environment using a tensile tester (product name: “Tensilon”). The value (N / 25 mm) measured under the condition of a peeling angle of 180 ° was defined as the adhesive strength.

The adherends used for the measurement of adhesive strength are as follows ([] indicates abbreviations in Table 2).
Stainless plate [SUS304]: SUS304 steel plate, No. 360 polishing, 150 mm × 70 mm × 0.7 mm.
-Polymethacrylate plate [PMMA plate]: manufactured by Yuko Trading Co., Ltd., product name “Acrylite L Opal 432”, 150 mm × 70 mm × 2 mm.
Float glass plate [Glass]: manufactured by Yuko Trading Co., Ltd., product name “float glass plate R3202 thread surface processing”, 150 mm × 70 mm × 2 mm.
Polyethylene plate [PE plate]: manufactured by Yuko Trading Co., Ltd., product name “PE (Kobe Poly Sheet) EL-N-AN”, 150 mm × 70 mm × 2 mm.
The results are shown in Table 2 below.
In the table, “AT” represents that an interfacial fracture has occurred between the adhesive and the substrate, “Cf” represents that cohesive fracture has occurred, and “Zip” represents zipping (smoothly It means that a state in which a horizontal line enters after peeling without peeling) occurs.

(Retention force test)
The obtained adhesive sheets 1 to 5, 1r to 4r are cut into a size of 25 mm × 100 mm, and a stainless plate so as to have a pasting area of 25 mm × 25 mm in an environment of 23 ° C. and 50% RH (relative humidity). It was affixed to (SUS304 steel plate, No. 360 polishing). At the time of pasting, a roller having a weight of 2 kg was used and reciprocated five times so as to be pressure-bonded to the adherend. After leaving for 20 minutes after sticking, it is transferred into an oven at a temperature of 40 ° C. and 80 ° C., a 1 kg weight is attached to the adhesive sheet so that a vertical load is applied, and the adhesive sheet is left in the oven. The elapsed time (seconds) until complete peeling from the adherend was measured. However, when the deviation did not fall out even after 70000 seconds had elapsed, the length of deviation (deviation (mm)) was measured. The longer the elapsed time until peeling off and the shorter the length of slipping off, the better the holding power.
In the table, “NC” means that there is no deviation.

(Probe tack test)
The obtained pressure-sensitive adhesive sheets 1 to 5 and 1r to 4r were cut into a size of 25 mm × 25 mm, and the probe tack measuring device (manufactured by RHESCA, product name “under the environment of 23 ° C. and 50% RH (relative humidity)”). PROBE TACK TESTER model RPT100 ”) and measured according to“ JIS Z0237: 1991 Reference 5 ”. Specifically, the release sheet of the measurement sample was peeled off, and a stainless steel probe having a diameter of 5 mm was brought into contact with the exposed adhesive surface for 1 second at a contact load of 0.98 N / cm ^2. Separated from the measurement sample at a speed of minutes, the force [N] peeled off at that time was measured.

From Table 2, the pressure-sensitive adhesive sheets 1 to 5 produced using the polysilsesquioxane graft copolymer of the present invention have excellent adhesive strength and various adhesives without using a crosslinking agent. It can be seen that it has a holding power at high temperatures.
The pressure-sensitive adhesive sheets (Examples 3 to 5) prepared using polysilsesquioxane graft copolymer obtained by reacting BA after ACMO use a copolymer obtained by reacting ACMO after BA. The adhesive strength superior to the PE plate is exhibited as compared with the pressure-sensitive adhesive sheet produced in Example (Example 2).

  On the other hand, the pressure-sensitive adhesive sheet 1r (Comparative Example 9) using the polysilsesquioxane graft polymer obtained without using ACMO was inferior in adhesive strength and holding power. The pressure-sensitive adhesive sheet 2r (Comparative Example 10) using a copolymer of BA and ACMO was inferior in holding power. The pressure-sensitive adhesive sheet 3r (Comparative Example 11) using the polysilsesquioxane graft copolymer obtained by using the same amount of ACMO as that of BA did not exhibit adhesive strength. The pressure-sensitive adhesive sheet 4r using MMA instead of ACMO (Comparative Example 12) was inferior in adhesive strength and holding power at high temperatures.

Claims (13)

In the molecule, the following formula (i) and / or (ii) and / or (iii)

[Wherein, D represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a combination thereof, R ¹ represents a hydrocarbon group, and R ² represents a hydrogen atom or a carbon atom having 1 to ² carbon atoms. 18 represents an alkyl group, and R ³ represents the formula (a)

(Wherein r ¹ represents a hydrocarbon group having 4 to 12 carbon atoms) and the formula (b)

(Wherein, r ² and r ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Moreover, even if r ² and r ³ are combined to form a ring, The ring may contain a heteroatom.), And the abundance ratio of the group represented by the formula (a) and the group represented by the formula (b) is a molar ratio. (Group represented by formula (a)) :( group represented by formula (b)) = 95: 5 to 60:40. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms, and k1, k2, and k3 are each independently Represents any natural number. ] A polysilsesquioxane graft copolymer having a repeating unit represented by the formula (provided that it contains at least one repeating unit among the repeating units represented by the formulas (ii) and (iii)) .) The group represented by the formula (b) has the following formula (b ′) in which r ² and r ³ together in the formula (b) form a ring that may contain a hetero atom.

The polysilsesquioxane graft copolymer according to claim 1, wherein the polysilsesquioxane graft copolymer is a group represented by the formula:   The polysilsesquioxane graft copolymer according to claim 1 or 2, which has a number average molecular weight of 50,000 to 500,000. In the formulas (ii) and (iii), the following formula

The repeating unit represented by the following formula (ca)

(R ² and r ¹ represent the same meaning as described above) and a block [A] composed of a repeating unit represented by the following formula (c-b):

(R ² , r ^2, and r ³ represent the same meaning as described above), and the block [A] and the block [B] are represented by the formula: − From the CH moiety side of the group represented by CH (R ⁴ ) -D-, the block array arranged so as to be-[B]-[A] or-[A]-[B]-[A] It has a polymer structure, The polysilsesquioxane graft copolymer in any one of Claims 1-3 characterized by the above-mentioned. In the formulas (ii) and (iii), the following formula

The repeating unit represented by the following formula (ca)

(R ² and r ¹ represent the same meaning as described above) and the following formula (c-b)

(R ^2, r ² and r ³ represent. The same as defined above) according to claim 1, characterized in that it comprises a random copolymer structure composed of a repeating unit represented by the Polysilsesquioxane graft copolymer. In the molecule, the following formula (i) and / or (ii-a) and / or (iii-a)

(In the formula, D represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a combination thereof, R ¹ represents a hydrocarbon group, R ⁴ represents a hydrogen atom, and 1 carbon atom. Represents an alkyl group having 6 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms in total, or an acyl group having 2 to 20 carbon atoms in total, X is an alkoxy group having 1 to 20 carbon atoms which may have a substituent, optionally substituted aryl group having 6 to 20 carbon atoms, or polysilsesquioxane compound having a repeating unit represented by the representative.) the amino group which may have a substituent ( However, it is limited to those containing at least one repeating unit among the repeating units represented by the formulas (ii-a) and (iii-a)).
Formula (1a): CH ₂ = C (R ^2a ) (R ^3a ) [wherein R ^2a represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R ^3a represents formula (a)

(Wherein r ¹ represents a hydrocarbon group having 4 to 12 carbon atoms). And the compound (1a) represented by the formula (1b): CH ₂ ═C (R ^2b ) (R ^3b ) [wherein R ^2b represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R ^3b is a group represented by the formula (b)

(R ² and r ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Further, r ² and r ³ may be combined to form a ring, The ring may contain a hetero atom.)). The compound (1b) represented by the formula (1b) is used at a molar ratio of (compound (1a)) :( compound (1b)) = 95: 5 to 60:40. Used in the graft polymerization reaction in the presence of a radical polymerization initiator,
In the molecule, formula (i) and / or (ii) and / or (iii)

(Wherein, ^D, R 1, ^{R 2,} and .R ^{3 R 4} is representing the same meaning as above, represents the ^{R 3a} or ^{R 3b,} k1, k2 and k3 are each independently any Represents a natural number, and when k1, k2 or k3 is 2 or more, groups represented by the formula: —CH ₂ —C (R ² ) (R ³ ) — may be the same or different. A polysilsesquioxane graft copolymer having a repeating unit represented by formula (ii), wherein the repeating unit represented by formulas (ii) and (iii) contains at least one repeating unit. Limited manufacturing method ) .


  The production method according to claim 6, wherein azobisisobutyronitrile is used as the radical polymerization initiator.   8. The polysilsesquioxane compound is graft-polymerized with the compound (1b) in the presence of a radical polymerization initiator, and then the compound (1a) is graft-polymerized. A process for producing the polysilsesquioxane graft copolymer described in 1.   In the presence of a radical polymerization initiator in the polysilsesquioxane compound, the molar ratio of the compound (1a) to the compound (1b) is (compound (1a)) :( compound (1b)) = 95: 5 The production of the polysilsesquioxane graft copolymer according to claim 6 or 7, wherein a mixture of the compound (1a) and the compound (1b) contained in a ratio of -60: 40 is graft-polymerized. Method. As a compound represented by the formula (1b), in the formula (1b), R ^2b represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R ^3b represents r ² in the formula (b), The following formula (b ′) in which r ³ together form a ring that may contain a hetero atom:

The production method according to claim 6, wherein a compound that is a group represented by the formula:   The production method according to any one of claims 6 to 10, wherein a polysilsesquioxane graft copolymer having a number average molecular weight of 50,000 to 500,000 is produced.   A pressure-sensitive adhesive comprising the polysilsesquioxane graft copolymer according to claim 1.   A pressure-sensitive adhesive sheet comprising a base material sheet and a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive according to claim 12 formed on the base material sheet.