JP2011178828A - Antistatic release agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a release agent capable of forming a releasing layer which has good releasability and develops superior antistatic performance. <P>SOLUTION: This antistatic release agent composition includes a releasable component, an antistatic component, and an electrolytic component, wherein the composition includes an organopolysiloxane represented by a specific formula as the antistatic component. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel antistatic release agent composition.

  As the release agent, generally, a silicone composition containing an alkenyl group-containing organopolysiloxane and an organopolyhydrogensiloxane is used. This is subjected to addition polymerization in the presence of a platinum catalyst to form a cured film having a peeling force for various adhesives. Usually, for example, it is used as a release film obtained by applying a release agent to a substrate such as paper, laminated paper, or plastic film and thermally curing it.

  Release films produced using release agents are generally cast film forming process films such as polyurethane resin, polyacrylic resin, and polyvinyl chloride resin, protective film for adhesive layer of adhesive film, green sheet of multilayer ceramic capacitor It is used as a molding process film.

  Conventionally, as a release film, what formed the release layer by apply | coating a silicone composition to the surface of a base film is generally known. However, as can be seen from the silicone main chain bond and the side chain structure, the coating film made of the silicone composition has a drawback that it does not leak charges and is very easily charged. The release film is in an environment where it is easily triboelectrically charged by contacting with various rolls or conveyors in processes such as conveyance, cutting, and printing, and further has a problem of causing charge when peeled from the release film. .

  Such static electricity failure, especially when stacking and storing resin sheets, etc., in addition to the problem that the resin sheets are repelled or stuck together due to electrical repulsion regardless of before and after peeling from the release film. In the case of an adhesive film, it causes a problem that foreign matters such as dust adhere to the adhesive layer. Moreover, there also arises a problem that application spots are likely to occur on the pressure-sensitive adhesive applied to the surface of the release film. From the above viewpoint, the release film needs to be subjected to antistatic treatment.

  As a film that can solve the above-mentioned problem of electrostatic interference, a release film in which a surfactant-based antistatic agent is directly added to a release layer is known (Patent Document 1). However, when a surfactant is selected as an antistatic agent, the ionic species (amine, phosphorus, sulfur, lead) coordinate with the platinum catalyst involved in the silicone addition reaction, causing catalyst poisoning and insufficient polymerization. . For this reason, even if it exhibits antistatic performance, it causes problems such as a decrease in adhesion and a decrease in peelability between the base film and the release layer. In addition, bleed is also a problem in cases other than ionic species that do not cause catalyst poison. In the first place, even if an antistatic agent is mixed in silicone, it will bleed on the surface and transfer to the pressure-sensitive adhesive will be a problem, and the compatibility with silicone will be poor and uneven dispersion will occur, causing unevenness in the crosslinking density. The adhesion of the release layer is lowered and the peeling performance is also lowered.

  As another means, there has been proposed a release film characterized in that a release layer is provided on one surface of a base film and an antistatic layer is provided on the other surface (Patent Document 2). . However, since this is a release film provided with an antistatic layer on the surface opposite to the release layer, there is a problem that the antistatic performance is insufficient to suppress peeling charge.

  Furthermore, a release film is known in which an antistatic layer is formed on the surface of a substrate film, and a release layer is laminated on the antistatic layer (Patent Document 3 and Patent Document 4). However, in the case of a release film in which a release layer is provided on an antistatic layer, if priority is given to peelability, the antistatic performance may be reduced, or depending on the antistatic agent, the release layer may become cloudy or fall off. There is. Furthermore, applying two layers to the substrate is disadvantageous in terms of cost because it requires at least two steps. In the case of two layers, since the silicone layer is present on the surface layer, the pressure-sensitive adhesive film that is the release surface is strongly negatively charged when the release film is peeled off. That is, even if the release film itself can be made non-charged, the surface to be released cannot be made completely uncharged, so that it is not put to practical use.

  In addition, a method of directly adding a fine particle body such as carbon nanotube (CNT) or a conductive polymer such as polypyrrole without dividing the antistatic layer and the release layer into two layers has been attempted (patent) Reference 5). However, in addition to the very difficult dispersion method of CNT, since the film is colored with an addition amount for sufficiently exhibiting the antistatic performance, there remains a problem in practical use. Moreover, the binder for fixing CNT or a conductive polymer in a mold release layer is used together. Since this binder is generally poor in compatibility with the release layer polyorganosiloxane, even if an attempt is made to design one layer without separating the release layer and the antistatic layer, the binder actually causes uneven distribution or separation, A problem such as peeling occurs between the release layer and the binder resin component, and the adhesion strength of the release layer decreases.

JP 10-44336 A JP-A-11-157013 JP 2000-52495 A JP 2005-153250 A JP2008-49542

  Accordingly, a main object of the present invention is to provide a release agent that can form a release layer that exhibits excellent antistatic performance while having good peelability and the like.

  As a result of intensive studies in view of the problems of the prior art, the present inventors have found that the above object can be achieved by employing a composition containing a specific antistatic component as a release agent, and the present invention has been completed. It came to do.

That is, the present invention relates to the following antistatic release agent composition.
1. A release agent composition comprising a releasable component, an antistatic component and an electrolyte component,
An antistatic release agent composition comprising an organopolysiloxane represented by the general formula (1) as the antistatic component;
[R ¹¹ represents a monovalent organic group. X _AB is a constituent part formed by bonding 0 to 100 monomer units A and 1 to 100 monomer units B with a siloxane bond in an arbitrary arrangement order. Monomer unit A is represented by general formula (1-1), and monomer unit B is represented by general formula (1-2);
(In the general formulas (1-1) and (1-2), R ¹¹ represents a monovalent organic group. R ¹² represents an alkylene group. R ¹⁵ represents a hydrogen atom or a monovalent organic group. Y _CD is a 0-100 or 0-100 amino monomer units D of the monomer unit C is a component comprising linked by an ether bond in any arrangement order from each other. monomer unit C ^{[-R 13} O -] (Wherein R ¹³ represents an alkylene group), and monomer unit D is represented by [-R ¹⁴ O-] (where R ¹⁴ represents an alkylene group) Monomer unit C and monomer Unit D is different from each other, and both cannot be zero at the same time.)].
2. Item 2. The antistatic release agent composition according to Item 1, wherein the release component comprises a component that is cured by addition polymerization of an alkenyl group and a SiH group.
3. Item 1. The releasable component comprises 1) an organopolysiloxane having at least two alkenyl groups in one molecule and 2) an organohydrogenpolysiloxane having at least two SiH groups in one molecule. The antistatic release agent composition as described.
4). Item 2. The antistatic property according to item 1, wherein the releasable component comprises 1) a compound represented by the following general formula (2) and 2) an organohydrogenpolysiloxane represented by the following general composition formula (3). Release agent composition;
[Wherein, R ^{A1 to} R ^A10 are the same as or different from each other and each represents an alkyl group, a cycloalkyl group, or an aryl group, and a part or all of the hydrogen atoms bonded to the carbon atom are substituted with a halogen atom or a cyano group. It is good. R ^{A11 to} R ^A15 are the same as or different from each other, and represent an alkenyl group.
a1, b1, c1, d1 and e1 are the same or different from each other and are positive integers, and at least one of b1, c1, d1 and e1 may be 0. α and β are the same or different from each other and are 0, 1, 2, or 3. ]
[Wherein, R ^A16 represents an alkyl group, a cycloalkyl group, or an aryl group, and a part or all of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom or a cyano group. f is a real number satisfying 0 ≦ f ≦ 3, g is a real number satisfying 0 <g ≦ 3, and satisfies 1 ≦ f + g ≦ 3. ]
5. An antistatic release film comprising a release layer obtained from the antistatic release agent composition according to any one of Items 1 to 4.
6). Item 6. The antistatic release film according to Item 5, wherein the release layer is obtained by curing a coating film of the antistatic release agent composition by heating.

  Since the antistatic release agent composition of the present invention contains a specific antistatic component in the release composition (silicone composition), the catalyst poison, bleed, etc., as found in the prior art. Since the problem can be effectively suppressed or prevented, it is possible to form a release layer that exhibits excellent antistatic performance as well as good peelability. That is, the release layer of the antistatic release agent composition of the present invention can prevent charging due to peeling or friction, and can exhibit good peelability from the peeled surface.

  In particular, in the past, when a glassy component such as a specific silicone composition (for example, a composition containing the component A described later) is used as the releasable composition, The combined use of the above components has generally been avoided because of problems such as bleed due to poor compatibility, but unexpectedly, the antistatic component of the present invention hardly causes such a problem, so excellent peelability And antistatic performance can both be achieved.

  For the same reason, when the release layer is formed on a base film and used, excellent performance in adhesion to the base film can be exhibited. Thereby, it is also possible to provide an excellent release film (release paper). That is, a release film including a release layer made of the antistatic release agent composition of the present invention on a base film can be provided.

  Furthermore, since the release layer has both excellent releasability and antistatic performance, it is possible to omit the formation of an antistatic layer and a release layer that are separately required. That is, it is also possible to constitute a two-layer type release film of a release layer by the base film and the antistatic release agent composition of the present invention. Thereby, a release film thinner than before can be provided.

  The antistatic release agent composition of the present invention or the release layer (or release film) formed using the same can be used in the same applications as conventional release agents or release films. That is, it can be suitably used as a release film that is laminated on the material in order to protect the surface of the material and then peeled off when the material is used. More specifically, process film for cast film formation of polyurethane resin, polyacrylic resin, polyvinyl chloride resin, etc., protective film for adhesive layer of adhesive film, process film for green sheet molding of multilayer ceramic capacitor, and other cast film formation It can be suitably used as a process film.

1. Antistatic Release Agent Composition The antistatic release agent composition of the present invention (the composition of the present invention) is a release agent composition comprising a release component, an antistatic component and an electrolyte component,
An antistatic release agent composition comprising an organopolysiloxane represented by the general formula (1) as the antistatic component;
[R ¹¹ represents a monovalent organic group. X _AB is a constituent part formed by bonding 0 to 100 monomer units A and 1 to 100 monomer units B with a siloxane bond in an arbitrary arrangement order. Monomer unit A is represented by general formula (1-1), and monomer unit B is represented by general formula (1-2).
(In the general formulas (1-1) and (1-2), R ¹¹ represents a monovalent organic group. R ¹² is the same as or different from each other and represents an alkylene group. R ¹⁵ represents a hydrogen atom or a monovalent organic group. In particular, Y _CD is preferably a hydrogen atom, and YCD is composed of 0 to 100 monomer units C and 0 to 100 monomer units D bonded to each other by an ether bond in an arbitrary arrangement order. The monomer unit C is represented by [—R ¹³ O—] (where R ¹³ represents an alkylene group), and the monomer unit D is represented by [—R ¹⁴ O—] (where R ¹⁴ is alkylene). The monomer unit C and the monomer unit D are different from each other, and they are not 0 at the same time.)]

Hereinafter, components of the composition of the present invention will be described.
Releasable component (component A)
The releasable component is not particularly limited, and any releasable component used in a known release agent can be used, but in particular, an addition-type silicone release agent can be suitably used. . That is, it is preferable to use a composition containing a release agent component that is cured by addition polymerization.

  More specifically, a composition that can be cured by addition polymerization of an alkenyl group and a SiH group is preferably used as the releasable component. A commercial item can also be used as such a mold release agent. For example, product names “KS-847T”, “KS-774”, “KS-3703” (silicone composition, both manufactured by Shin-Etsu Chemical Co., Ltd.), “SD7226”, “LTC750A” (silicone composition, both Toray Dow Corning Co., Ltd.).

  As described above, by adopting a composition that can be cured by addition polymerization of an alkenyl group and a SiH group, compounds having various chemical structures can be widely used as the antistatic component (component B) of the present invention. For example, when a compound group that causes a condensation reaction between an isocyanate group and a hydroxyl group is used as a release component, if an antistatic component having a hydroxyl group at the terminal is used, the isocyanate group and the antistatic component react preferentially, There is a possibility that cross-linking inhibition, lowering of adhesion to the substrate, and the like may occur. On the other hand, when a composition that can be cured by addition polymerization of an alkenyl group and a SiH group is used as the releasable component, the above-described phenomenon hardly occurs, so that a desired effect can be obtained more reliably.

Examples of the addition type silicone release agent as described above include 1) organopolysiloxane having at least two alkenyl groups in one molecule (A _one component) and 2) at least two in one molecule (preferably , A composition containing an organohydrogenpolysiloxane (A ₂ component) having at least three SiH groups can be suitably employed. This makes it possible to A ₂ component with respect to A ₁ component as a main agent plays a role as a crosslinking agent, to form a silicone release layer having a desired peel resistance. That is, it by adopting this two-component system, an alkenyl group of the organopolysiloxane, curing the curable silicone composition of the addition reaction type (addition polymerization) by reacting with SiH groups of A ₂ component As a result, a desired silicone release layer can be more effectively formed. Since alkenyl group of A ₁ component is less than two in one molecule which may curability can not be formed of the desired silicone release layer decreases, at least two alkenyl groups per molecule in A ₁ component It is preferable to have. For the same reason, it is preferable to have at least two SiH groups as the A ₂ component per molecule. Such A ₁ component and A ₂ components, as follows can be exemplified.

(A ₁ component)
The A ₁ component can be preferably used a compound represented by the following general formula (2).
[Wherein, R ^{A1 to} R ^A10 are the same as or different from each other and each represents an alkyl group, a cycloalkyl group, or an aryl group, and a part or all of the hydrogen atoms bonded to the carbon atom are substituted with a halogen atom or a cyano group. It is good. R ^{A11 to} R ^A15 are the same as or different from each other, and represent an alkenyl group.
a1, b1, c1, d1, and e1 are the same or different from each other and are positive integers, and b1, c1, d1, and e1 may be 0. α and β are the same or different from each other and are 0, 1, 2, or 3. ]

R ^{A1 to} R ^A10 are the same as or different from each other and represent an alkyl group, a cycloalkyl group, or an aryl group, and a part or all of the hydrogen atoms bonded to the carbon atoms of these groups are halogen atoms or cyano. It may be substituted with a group. The alkyl group preferably has 1 to 20 carbon atoms including a substituent. The cycloalkyl group preferably has 3 to 20 carbon atoms including a substituent. The aryl group preferably has 6 to 20 carbon atoms including a substituent.

Specific examples of these R ^{A1 to} R ^A10 include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, Hexyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and other alkyl groups, cyclopropyl, cyclobutyl Group, a cycloalkyl group such as cyclopentyl group and cyclohexyl group, and an aryl group such as phenyl group, tolyl group, xylyl group and naphthyl group. Examples of the group in which part or all of the hydrogen atoms bonded to the carbon atoms of these hydrocarbon groups are substituted with halogen atoms or cyano groups include, for example, chloromethyl group, 2-bromoethyl group, 3,3,3-trimethyl group. A fluoropropyl group, a p-chlorophenyl group, a 2-cyanoethyl group and the like can be mentioned.

In the present invention, as R ^{A1 to} R ^A10 , an alkyl group having 1 to 20 carbon atoms is preferable, and a part or all of R ^{A1 to} R ^A10 is more preferably a methyl group. For ^example, more than 80% of the total number of groups R ^{A1 to R A10} can be suitably used _{A 1} component is a methyl group. In particular, it is more preferable that all of R ^{A1 to} R ^A10 are methyl groups.

R ^{A11 to} R ^A15 are the same as or different from each other, and represent an alkenyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, and a heptenyl group. In the present invention, the alkenyl group of R ^{A11 to} R ^A15 is particularly preferably a vinyl group. That is, it is more preferable that a part or all of R ^{A11 to} R ^A15 are vinyl groups.

A1, b1, c1, d1, and e1 are the same or different from each other and are positive integers, and at least one of b1, c1, d1, and e1 may be zero. In particular, a1, b1, c1, d1, and e1 have an organopolysiloxane (A ₁ ) viscosity at 25 ° C. of 0.05 Pa · s or more, and a 25% toluene solution of the organopolysiloxane (A ₁ ) at 25 ° C. It is preferable that the viscosity is 0.002 to 30 Pa · s, particularly 0.005 to 20 Pa · s. By employing the A ₁ component having such a viscosity, it is possible to form a layer of more uniform thickness on a substrate film, it is possible to increase the workability during coating. From this standpoint, a1, b1, c1, d1 and e1 are desirably positive numbers satisfying 28 ≦ a1 + b1 × (d1 + e1 + 2) + c1 ≦ 10000 from the standpoint of the above-described viscosity and the like.

  The α and β are the same or different from each other and are 0, 1, 2, or 3. However, it is preferable that b1 × (e1 + β) + c1 + 2 × α ≧ 2. When satisfying such a relationship, an organosiloxane structure having at least two alkenyl groups in one molecule is obtained, and the effect of film formation by addition reaction with SiH groups can be more reliably obtained.

The alkenyl group of the organopolysiloxane (A ₁ ) reacts with the SiH group of the crosslinking agent (A ₂ ) described later to cure, but the organopolysiloxane needs at least two alkenyl groups per molecule. If it is less than 2, the curability of the silicone composition may be lowered, and a desired silicone release layer may not be formed.

  In the present invention, in particular, in the formula (2), it is preferable that the total number b1 × (e1 + β) + c1 + 2 × α of one molecule has a range of 2 to 150. If it is less than the said lower limit, sclerosis | hardenability of a silicone composition may fall and a desired silicone release layer may not be formed. On the other hand, when the upper limit is exceeded, the non-adhesiveness of the silicone release layer may be reduced.

Specific examples of A ₁ component in the present invention, may include compounds represented by the following formula. A known or commercially available compound can also be used.

(A ₂ component)
As the A ₂ component, an organohydrogenpolysiloxane represented by the following general composition formula (3) can be suitably used.
[Wherein, R ^A16 represents an alkyl group, a cycloalkyl group or an aryl group, and a part or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a halogen atom or a cyano group. It is. ]

  The alkyl group preferably has 1 to 20 carbon atoms including a substituent. The cycloalkyl group preferably has 3 to 20 carbon atoms including a substituent. The aryl group preferably has 6 to 20 carbon atoms including a substituent.

As specific examples of these groups, the same groups as those described for R ^{A1 to} R ^A10 can be used. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, 1-ethylpentyl group Alkyl groups such as octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group; cycloalkyl such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. Groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; Examples of the group in which part or all of the hydrogen atoms bonded to the carbon atoms of these hydrocarbon groups are substituted with halogen atoms or cyano groups include, for example, chloromethyl group, 2-bromoethyl group, 3,3,3-trimethyl group. A fluoropropyl group, a p-chlorophenyl group, a 2-cyanoethyl group and the like can be mentioned.

In the present invention, as R ^A16 , among these, an alkyl group having 1 to 20 carbon atoms is preferable, and a methyl group is more preferable.

  The f is a real number that satisfies 0 ≦ f ≦ 3, and g is a real number that satisfies 0 <g ≦ 3, and satisfies 1 ≦ f + g ≦ 3.

  As described above, such an organohydrogenpolysiloxane preferably has at least two, especially three or more SiH groups in one molecule.

The molecular structure of the organohydrogenpolysiloxane may be linear, branched, or cyclic. In particular, the viscosity of the _{A 2} component (25 ° C.), the number mPa · s to several tens of thousand mPa · s, in particular 1~20000mPa · s, further particularly 5~10000mPa · s. Such A ₂ component having a viscosity can be further enhanced coatability to a substrate film by employing a.

As specific examples of the organohydrogenpolysiloxane used as the A ₂ component, those represented by the general formulas (4) to (8) can be suitably used. These may be known or commercially available as a crosslinking agent for addition reaction type silicone resins.
[H to w in the general formulas (4) to (8) are integers in the range shown below. h, l and n are the same or different and are an integer of 3 to 500, m, p and u are the same or different and are an integer of 1 to 500, i, j, k, o, q, r, s, t, v and w are mutually the same or different and are integers of 0-500. ]

A ₂ component, the number of moles of the SiH groups, it is preferable that the content as corresponds to 1 to 5 times the number of moles of alkenyl groups contained in A ₁ component. In general, the amount may be 0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight, _per 100 parts by weight of A component. When the number of moles of SiH groups is less than the lower limit, the cross-linking due to the addition reaction of alkenyl groups and SiH groups is not sufficient, and the non-adhesiveness of the silicone release layer formed from the cured product of the silicone composition is lowered. There is a fear. On the other hand, even if the content exceeds the upper limit, a corresponding increase in the effect is not observed, and not only the cost performance is lowered, but the composition may change over time.

Antistatic component (component B)
As the antistatic component in the composition of the present invention, an organopolysiloxane represented by the general formula (1) is used. Such organopolysiloxane itself may be a known or commercially available one. For example, product names “KF-354”, “KF-355”, “KF-945” (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be suitably used.
[R ¹¹ represents a monovalent organic group. X _AB is a constituent part formed by bonding 0 to 100 monomer units A and 1 to 100 monomer units B with a siloxane bond in an arbitrary arrangement order. Monomer unit A is represented by general formula (1-1), and monomer unit B is represented by general formula (1-2).
(In the general formulas (1-1) and (1-2), R ¹¹ represents a monovalent organic group. R ¹² is the same as or different from each other and represents an alkylene group. R ¹⁵ represents a hydrogen atom or a monovalent organic group. Y _CD is particularly preferably a hydrogen atom, and YCD is a structure in which 0 to 100 monomer units C and 0 to 100 monomer units D are bonded to each other by an ether bond in an arbitrary arrangement order. The monomer unit C is represented by [—R ¹³ O—] (where R ¹³ represents an alkylene group), and the monomer unit D is represented by [—R ¹⁴ O—] (where R ¹⁴ is an alkylene group). The monomer unit C and the monomer unit D are different from each other, and both do not become 0 at the same time.)].

Examples of the monovalent organic group of R ¹¹ include monovalent organic groups having a C 1-4 alkyl group such as a methyl group, an ethyl group, and a propyl group, and C 6-8 such as a phenyl group and a tolyl group. A monovalent organic group having a C 7-9 aralkyl group such as a monovalent organic group having an aryl group, a benzyl group, or a phenethyl group, each of which may have a substituent such as a hydroxyl group.

Examples of the alkylene group of R ¹² , R ¹³ and R ¹⁴ include an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group and a propylene group. R ¹² , R ¹³ and R ¹⁴ are They may be the same or different.

R ¹³ and R ¹⁴ are alkylene groups, and at least one of them is preferably an ethylene group or a propylene group from the viewpoint of the solubility of the electrolyte salt.

R ¹⁵ is, for example, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or a monovalent organic group exemplified by an acyl group such as an acetyl group or a propionyl group, You may have a substituent. R ¹⁵ may be a hydrogen atom.

  In the above formula, the arrangement order of the monomer unit A and the monomer unit B and the arrangement order of the monomer unit C and the monomer unit D are arbitrary. Thus, for example, the respective monomer units can be arranged in blocks or randomly.

As the component B in the present invention, more specifically, for example, a compound represented by the following general formula (9) can be used.
In the formula, R ^B1 represents a monovalent organic group, R ^{B2 to} R ^B4 represent an alkylene group, and R ^B5 represents a hydrogen atom or a monovalent organic group. x is an integer of 0 to 100, and y is an integer of 1 to 100. The arrangement order of the —Si (R ^B1 ) ₂ —O— unit and the —Si (R ^B1 ) (R ^B2 O —) — O— unit is arbitrary. z and aa are the same or different from each other, and are each an integer of 1 to 100, and are not 0 at the same time. The arrangement order of the -R ^B3 O- unit and the -R ^B4 O- unit is arbitrary.

The organic group of R ^B1 is the same as R ¹¹ , the alkylene group of R ^{B2 to} R ^B4 is the same as R ^{12 to} R ^14, and the organic group of R ^B5 is the same as R ¹⁵ It is. More specifically, for example, a compound in which R ^B1 is a methyl group, R ^{B2 to} R ^B4 are ethylene groups or propylene groups, and R ^B5 is a hydrogen atom can be preferably used.

  The B component is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the A component. If the amount is less than 0.5 part by weight, the antistatic performance of the obtained release layer may be insufficient. On the other hand, when the amount exceeds 20 parts by weight, the release layer is not sufficiently crosslinked, and the hardness of the coating film cannot be obtained, and the adhesion may be lowered.

Electrolyte component (C component)
The electrolyte component (C component) is not particularly limited as long as it is an ion conductive electrolyte salt compound. For example, a metal salt of an inorganic acid or an organic acid can be used. More specifically, an electrolyte component composed of the following cation and anion can be preferably used.

  Examples of the cation include alkali metal ions such as sodium, potassium, lithium and cesium, and alkaline earth metal ions such as magnesium and calcium.

  Examples of the anions include perhalogenate anions such as perchloric acid and perbromate, halogen anions such as chlorate and bromate, halogen anions such as chlorine and bromine, alkyl sulfones such as octyl sulfonate and stearyl sulfonate. Acid anions, aryl sulfonate anions such as dodecylbenzene sulfonate and benzene sulfonate, alkyl sulfate anions such as lauryl sulfate and ethyl sulfate, carboxylate anions such as sulfate anion, acetic acid and propionic acid, alkyl phosphate anions and phosphate anions , Phosphite anion, nitrate anion, carboxylic acid anion, halide anions such as tetrafluoroboron, hexafluoroarsenic, hexafluorolin, perfluoroalkylsulfonic acid such as trichloromethanesulfonic acid, trifluoromethanesulfonic acid, bistri Le Oro bis perfluoroalkylsulfonylimide acids such as methane sulfonyl imide acid, trichloroacetic acid, an organic acid anion having a halogenated alkyl, such as trifluoroacetic acid, thiocyanate anions, tetraphenylboron anions and the like.

  In the present invention, among these, at least one of 1) lithium salt, sodium salt and potassium salt of perfluoroalkylsulfonic acid and 2) lithium salt, sodium salt and potassium salt of bisfluoromethanesulfonylimidic acid is preferably used. be able to.

The content of the electrolyte component is not limited, but in particular, (number of moles of component B) × (number of —R ¹³ O-group and —R ¹⁴ O-group in one molecule of component B) is [R ¹³ O + R. ¹⁴ O], which is expressed as a temporary number of moles of the B component as viewed from the -R ¹³ O-group and the -R ¹⁴ O-group, from the viewpoint of antistatic effect and transparency, [R ¹³ O + R ^[14 O] is preferably 0.005 to 1.5 mole times.

Other Components In the composition of the present invention , components added to known release agents can be appropriately blended. For example, a solvent, a catalyst, etc. can be mentioned.

  As the catalyst, a catalyst for polymerizing the silicone-based release component can be used. As such a catalyst, in the case of an addition type silicone release agent, a known platinum catalyst or titanium oxide can be used as a catalyst. The content of the catalyst in the composition of the present invention is not particularly limited, but is usually about 0.1 to 10% by weight.

  Further, the solvent (solvent or dispersion medium) is not limited as long as it is used for preparing a release agent coating solution (solution type coating solution or emulsion type coating solution). In addition, an organic solvent such as toluene, hexane, ethyl acetate, methyl ethyl ketone, heptane or a mixture thereof is used as a diluent.

Preparation of the composition of the present invention The composition of the present invention can be obtained by uniformly mixing the components described above. What is necessary is just to mix uniformly using the said solvent etc. when setting it as a liquid type composition. Thereby, a solution type coating liquid or an emulsion type coating liquid can be prepared. In these coating liquids, a solvent is generally used as a diluent, and the viscosity can be adjusted. When a solvent is used, the solid content of the composition of the present invention may be about 0.1 to 10% by weight.

2. Antistatic Release Film The present invention includes an antistatic release film (present film) obtained by forming a coating film using the composition of the present invention and curing it by heating.

The method for forming the coating film is not particularly limited. For example, the composition of the present invention (coating liquid) may be applied to at least one surface of the base film. As the coating method, for example, a gravure coating method, a bar coating method, a multi-roll coating method, or the like can be employed. Coating amount is 0.01 to 10 g / ^{m 2} is suitable as solid content equivalent coating amount, it is preferable that the particular 0.03~1g / ^{m 2.}

  There is no restriction | limiting in particular in a base film, According to the use of various release films, it can select suitably from what was conventionally used as a base film of a release film. Examples of such a base film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene films, polypropylene films, polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, and ethylene-vinyl acetate. Polymer film, polystyrene film, polycarbonate film, polysulfone film, polyether ether ketone film, polyether sulfone film, polyphenylene sulfide film, polyether imide film, polyimide film, fluororesin film, polyamide film, acrylic resin film, norbornene resin Examples thereof include a film and a cycloolefin resin film.

  There is no restriction | limiting in particular in the thickness of this base film, Although it selects suitably according to the use of a release film, Usually, it is 10-150 micrometers, Preferably it is 20-120 micrometers.

  In addition, this base film is subjected to a surface treatment by an oxidation method, a concavo-convex method, or a primer treatment on one side or both sides for the purpose of improving the adhesion with a release agent layer provided on the surface. be able to. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Examples of the unevenness method include a sand blast method and a solvent treatment method. In addition, as the primer treatment, adhesion is improved by using a silane coupling agent alone, using a polyester resin, or using a specific resin and a silane coupling agent in combination. These surface treatment methods are appropriately selected according to the type of the base film, but in the present invention, the corona discharge treatment method is preferable.

  In this invention, you may use together the type of isocyanate compound which does not react with active hydrogen as a hardening | curing agent in a mold release agent composition. A blocked isocyanate compound is particularly desirable from the viewpoint of dispensing stability.

  The coating is then cured by heating. The heat treatment may be performed in a temperature range of about 70 to 160 ° C. The heating time should just ensure time until it fully hardens | cures according to a composition of this invention composition, the coating amount, etc. What is necessary is just to heat-process in the oven of a coating machine, for example.

  Thus, the thickness (thickness after drying) of the release agent layer formed from the antistatic release agent composition is not particularly limited, but uniform film properties, antiblocking properties, releasability and substrate From the viewpoint of adhesion to the film, etc., it is usually about 0.01 to 3 μm, and particularly preferably 0.05 to 1 μm.

  The features of the present invention will be described more specifically with reference to the following examples and comparative examples. However, the scope of the present invention is not limited to the examples.

Example 1
100 parts by weight of a silicone composition as a releasable component [manufactured by Shin-Etsu Chemical Co., Ltd., trade name KS-847T, (solid content 30% by weight)], catalyst [manufactured by Shin-Etsu Chemical Co., Ltd., trade name CAT- 5 parts by weight of PL-50T], 1.05 parts by weight of an organopolysiloxane containing an antistatic component polyalkylene chain [manufactured by Shin-Etsu Chemical Co., Ltd., trade name KF-354], perchlorate as an electrolyte salt compound 0.45 parts by weight of lithium acid was added, and 201.7 parts by weight of methyl ethyl ketone was added as a diluent, followed by stirring and mixing to prepare an antistatic release agent composition. This antistatic release agent composition was applied to a 38 μm thick polyester film [manufactured by Toyobo Co., Ltd., trade name E-5101] with a bar coater No. 3 (wet 6.87 μm), then heat treated at 140 ° C. for 1 minute to cure, antistatic release layer having a thickness of 0.10 μm and an antistatic agent concentration in the release coating of 5% by weight An antistatic release film having the following characteristics was prepared.

Example 2
100 parts by weight of a silicone composition as a releasable component [manufactured by Shin-Etsu Chemical Co., Ltd., trade name KS-774, (solid content 30% by weight)], catalyst [manufactured by Shin-Etsu Chemical Co., Ltd., trade name CAT- 5 parts by weight of PL-4], polyalkylene chain-containing organopolysiloxane [Shin-Etsu Chemical Co., Ltd., trade name KF-354] 1.05 parts by weight, trifluoromethane as electrolyte salt compound 0.45 parts by weight of lithium sulfonate was added, and 201.7 parts by weight of methyl ethyl ketone was added as a diluent and mixed by stirring to prepare an antistatic release agent composition. This antistatic release agent composition was applied onto a film in the same manner as in Example 1 to produce an antistatic release film.

Example 3
100 parts by weight of a silicone composition as a releasable component [manufactured by Shin-Etsu Chemical Co., Ltd., trade name KS-3703, (solid content 30% by weight)], catalyst [manufactured by Shin-Etsu Chemical Co., Ltd., trade name CAT- 5 parts by weight of PL-50T], polyalkylene chain-containing organopolysiloxane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name KF-355] of 1.05 parts by weight, bistrifluoro as an electrolyte salt compound 0.45 part by weight of methanesulfonylimide lithium was added, and 201.7 parts by weight of methyl ethyl ketone was added as a diluent, followed by stirring and mixing to prepare an antistatic release agent composition. This antistatic release agent composition was applied onto a film in the same manner as in Example 1 to produce an antistatic release film.

Example 4
100 parts by weight of silicone composition as a releasable component [manufactured by Toray Dow Corning Co., Ltd., trade name SD7226, (solid content 30% by weight)], catalyst [manufactured by Toray Dow Corning Co., Ltd., trade name SRX- 212] 5 parts by weight, polyalkylene chain-containing organopolysiloxane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name KF-945] 1.05 parts by weight, lithium perchlorate as electrolyte salt compound 0.45 part by weight was added, and 201.7 parts by weight of methyl ethyl ketone was added as a diluent, followed by stirring and mixing to prepare an antistatic release agent composition. This antistatic release agent composition was applied onto a film in the same manner as in Example 1 to produce an antistatic release film.

Example 5
100 parts by weight of silicone composition as a releasable component [manufactured by Toray Dow Corning Co., Ltd., trade name LTC750A, (solid content 30% by weight)], catalyst [manufactured by Toray Dow Corning Co., Ltd., trade name SRX- 212] 5 parts by weight, polyalkylene chain-containing organopolysiloxane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name KF-354] 1.05 parts by weight, lithium perchlorate as electrolyte salt compound 0.45 part by weight was added, and 201.7 parts by weight of methyl ethyl ketone was added as a diluent, followed by stirring and mixing to prepare an antistatic release agent composition. This antistatic release agent composition was applied onto a film in the same manner as in Example 1 to produce an antistatic release film.

Comparative Example 1
100 parts by weight of a silicone composition as a releasable component [manufactured by Shin-Etsu Chemical Co., Ltd., trade name KS-847T, (solid content 30% by weight)], catalyst [manufactured by Shin-Etsu Chemical Co., Ltd., trade name CAT- 5 parts by weight of PL-50T] and 1.50 parts by weight of a cationic surfactant as an antistatic component [manufactured by Maruhishi Oil Chemical Co., Ltd., trade name Denon 1826], and methyl ethyl ketone 201. as a diluent. 7 parts by weight was added and stirred and mixed to prepare an antistatic release agent composition. This antistatic release agent composition was applied onto a film in the same manner as in Example 1 to produce an antistatic release film.

Comparative Example 2
100 parts by weight of a silicone composition as a releasable component [manufactured by Shin-Etsu Chemical Co., Ltd., trade name KS-847T, (solid content 30% by weight)], catalyst [manufactured by Shin-Etsu Chemical Co., Ltd., trade name CAT- 5 parts by weight of PL-50T] and 1.50 parts by weight of an anionic surfactant [manufactured by Maruhishi Oil Chemical Co., Ltd., trade name Erimina 724] as an antistatic agent component, and methyl ethyl ketone 201. 7 parts by weight was added and stirred and mixed to prepare an antistatic release agent composition. This antistatic release agent composition was applied onto a film in the same manner as in Example 1 to produce an antistatic release film.

Test example 1
Various performances of the films obtained in Examples and Comparative Examples were evaluated. The results are shown in Table 1. In Table 1, “Blank” indicates a silicone composition that does not contain an antistatic component (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KS-774, (solid content 30% by weight)), catalyst [Shin-Etsu Chemical Co., Ltd. This is a release film prepared from 5 parts by weight of the product name CAT-PL-4]. In addition, about each performance in Table 1, evaluation was implemented by the following method.

(1) Evaluation of antistatic performance and transparency (1-1) Surface resistivity
The surface resistivity of the release film was measured according to JIS K6911 (TOA Electronics,
Ltd ULTRA MEGOHMMETER SM-8210).
(1-2) A charged voltage test A sample for measurement (5 cm × 5 cm) was cut out from the produced peeled film, mounted in a charged voltage measuring device (Static Honest Meter), and the surface was subjected to corona discharge (voltage 10 kV × 1 min). It was charged and the equilibrium voltage and half-life were measured. (Product name: STATIC HONESTMETER H-0110, manufactured by Sicid Electrostatic Co., Ltd.)
(1-3) Transparency The total light transmittance and haze were measured by an integrating sphere type spectral transmittance measuring method. (Made by Tokyo Denshoku, product name haze meter MODEL TC-H III)

(2) Performance evaluation as a release film (2-1) Adhesiveness The state when rubbed 5 times with a finger under a load of 500 g was observed. A case where no whitening or omission occurred was indicated as “◯”, and a case where any of them occurred was indicated as “X”.
(2-2) Peeling force Adhesive tape (31B tape, width 2.5 cm) manufactured by Nitto Denko Co., Ltd. was bonded to the peeling film under a load of 3 to 5 kg under an atmosphere of room temperature 23 ° C. and humidity 50%. After adjusting the humidity for 20 hours, the load when the peel strength was peeled off in the 180 ° direction at a peel speed of 0.3 m / min was measured with a universal tensile tester.
(2-3) Residual Adhesion Rate An adhesive tape (Nitto Denko Corporation, 31B tape, width 2.5 cm) was bonded to the release film, and pressure bonded at 20 g / cm ² for 20 hours. When this tape is peeled off from the release film, bonded to a stainless steel plate (SUS304, mirror-finished BA plate) with a rubber roller with a load of 2 kg, and peeled off at 180 ° in a universal tensile testing machine at a speed of 0.3 m / min. The adhesive strength of was measured. The standard was 31B tape and the adhesive strength to the SUS plate was 100%.
(Residual adhesion rate%) = (Peel strength of the tape bonded to the SUS plate after being once bonded to the release film) ÷ (Peel strength of the tape bonded to the SUS plate of unused tape) × 100 ( %)

  As is clear from the above results, it is understood that when a surfactant is used as the antistatic component, not only the antistatic performance is not sufficient, but also satisfactory results cannot be obtained in adhesion and the like. On the other hand, in Examples 1-5, it turns out that the mold release layer which can exhibit the antistatic performance which was excellent at the same time as peelability etc. is favorable.

Claims (6)

A release agent composition comprising a releasable component, an antistatic component and an electrolyte component,
An antistatic release agent composition comprising an organopolysiloxane represented by the general formula (1) as the antistatic component;
[R ¹¹ represents a monovalent organic group. X _AB is a constituent part formed by bonding 0 to 100 monomer units A and 1 to 100 monomer units B with a siloxane bond in an arbitrary arrangement order. Monomer unit A is represented by general formula (1-1), and monomer unit B is represented by general formula (1-2);
(In the general formulas (1-1) and (1-2), R ¹¹ represents a monovalent organic group. R ¹² represents an alkylene group. R ¹⁵ represents a hydrogen atom or a monovalent organic group. Y _CD is a 0-100 or 0-100 amino monomer units D of the monomer unit C is a component comprising linked by an ether bond in any arrangement order from each other. monomer unit C ^{[-R 13} O -] (Wherein R ¹³ represents an alkylene group), and monomer unit D is represented by [-R ¹⁴ O-] (where R ¹⁴ represents an alkylene group) Monomer unit C and monomer Unit D is different from each other, and both cannot be zero at the same time.)]. The antistatic release agent composition according to claim 1, wherein the release component comprises a component that is cured by addition polymerization of an alkenyl group and a SiH group. The releasable component comprises 1) an organopolysiloxane having at least two alkenyl groups in one molecule and 2) an organohydrogenpolysiloxane having at least two SiH groups in one molecule. The antistatic release agent composition as described. The antistatic property according to claim 1, wherein the releasable component comprises 1) a compound represented by the following general formula (2) and 2) an organohydrogenpolysiloxane represented by the following general composition formula (3). Release agent composition;
[Wherein, R ^{A1 to} R ^A10 are the same as or different from each other and each represents an alkyl group, a cycloalkyl group, or an aryl group, and a part or all of the hydrogen atoms bonded to the carbon atom are substituted with a halogen atom or a cyano group. It is good. R ^{A11 to} R ^A15 are the same as or different from each other, and represent an alkenyl group.
a1, b1, c1, d1 and e1 are the same or different from each other and are positive integers, and at least one of b1, c1, d1 and e1 may be 0. α and β are the same or different from each other and are 0, 1, 2, or 3. ]
[Wherein, R ^A16 represents an alkyl group, a cycloalkyl group, or an aryl group, and a part or all of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom or a cyano group. f is a real number satisfying 0 ≦ f ≦ 3, g is a real number satisfying 0 <g ≦ 3, and satisfies 1 ≦ f + g ≦ 3. ] The antistatic release film containing the release layer obtained from the antistatic release agent composition in any one of Claims 1-4. 6. The antistatic release film according to claim 5, wherein the release layer is obtained by curing a coating film made of an antistatic release agent composition by heating.