CN108659748B - Adhesive composition and surface protective film - Google Patents

Adhesive composition and surface protective film Download PDF

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Publication number
CN108659748B
CN108659748B CN201810472273.4A CN201810472273A CN108659748B CN 108659748 B CN108659748 B CN 108659748B CN 201810472273 A CN201810472273 A CN 201810472273A CN 108659748 B CN108659748 B CN 108659748B
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meth
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acrylate
weight
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CN108659748A (en
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长仓毅
岛口龙介
长谷川良
新见洋人
吉田弘幸
菱沼昌世
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesive Tapes (AREA)

Abstract

The invention provides an adhesive composition having antistatic performance, excellent balance of adhesive force at low peeling speed and high peeling speed, long storage period, and excellent durability and reworkability. The adhesive composition includes: (A) 100 parts by weight of a copolymer of (B) a hydroxyl group-containing copolymerizable monomer as a copolymerizable monomer group and at least one (meth) acrylate monomer having an alkyl group with a carbon number of C4 to C18; (C) 0.1 to 10 parts by weight of a bifunctional or higher isocyanate compound; (D) 0.001-0.5 part by weight of a crosslinking catalyst for the metal chelate; (E) 0.1 to 200 parts by weight of a keto-enol tautomer compound; and 0.05 to 5 parts by weight of an ionic compound having a melting point of 25 to 50 ℃ as an antistatic agent (F), and the ratio of (E)/(D) by weight is 70 to 700.

Description

Adhesive composition and surface protective film
The present invention is a divisional application having application No. 201510053170.0, application date 2015, 02, and the title "adhesive composition and surface protective film", which is based on japanese patent application No. JP2014-090580, 24/04/2014, and claims priority.
Technical Field
The present invention relates to an adhesive composition and a surface protective film. More particularly, the present invention relates to an adhesive composition for a surface protection film of a polarizing plate having antistatic properties, an excellent balance of adhesive strength at a low peeling rate and a high peeling rate, a long shelf life, and excellent durability and reworkability, and a surface protection film.
Background
From the viewpoint of excellent transparency, an acrylic adhesive comprising a copolymer obtained by copolymerizing an alkyl (meth) acrylate as a main component with an acrylic monomer having a hydroxyl group, a carboxyl group, or the like as a functional group is preferably used as the adhesive for optical use. Further, an adhesive having various physical properties such as adhesive strength properly adjusted is required. In particular, in order to be suitable for a production process in a factory, an adhesive for a surface protective film or the like is required to have an excellent balance of adhesive force at a low peeling speed and a high peeling speed suitable for bonding by an automatic bonding apparatus. Further, an adhesive which has a long pot life, and is excellent in durability, reworkability and antistatic property, in addition to the balance of adhesive force, is required.
Various physical properties of such a binder can be adjusted by performing a crosslinking reaction using an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, or the like that reacts with a functional group such as a hydroxyl group or a carboxyl group contained in an acrylic binder composed of a copolymer, thereby adjusting a binding power, an aggregating power, and the like.
Conventionally, isocyanate-based crosslinking agents have been generally used as crosslinking agents for acrylic adhesives. In addition, in the crosslinking reaction using an isocyanate-based crosslinking agent, a metal chelate is often used as a catalyst for accelerating the crosslinking reaction.
Generally, dibutyltin dilaurate, which is an organotin compound, is used as a catalyst for the crosslinking reaction from the viewpoint of excellent reaction rate of the crosslinking reaction, but the use of dibutyltin compounds has been avoided at present because of their harmful toxicity.
Therefore, a crosslinking catalyst which can be used in combination with an isocyanate-based crosslinking agent, can replace a dibutyltin compound, is inexpensive, and has an excellent reaction rate of a crosslinking reaction is required, but it is difficult to develop and obtain the catalyst.
In view of the above, patent document 1 discloses the following: as a crosslinking catalyst which can be used in combination with an isocyanate-based crosslinking agent, an iron chelate compound is preferable among metal chelate compounds; and is particularly preferable because of its excellent catalytic activity.
However, the acrylic adhesive composition containing the crosslinking catalyst slowly undergoes a crosslinking reaction even during standing at normal temperature. Therefore, in the industrial production of an adhesive, a crosslinking catalyst and a reaction inhibitor are generally used in combination in order to stop a crosslinking reaction from the time when a raw material of an adhesive composition is mixed until the crosslinking reaction is started.
Regarding the combined use of the crosslinking catalyst and the reaction inhibitor, patent document 2 discloses a method for producing a polyurethane using a reaction polyurethane mixture containing a catalyst system comprising a mixture of at least one metal acetylacetone and acetylacetone in a weight ratio of the metal acetylacetone to the acetylacetone of 2: 1.
The binder composition described in patent document 1 proposes the amount of a metal compound (crosslinking catalyst) added to a copolymer containing a hydroxyl group and a carboxyl group and having a (meth) acrylate as a constituent monomer unit, but does not describe the amount of a crosslinking inhibitor added. In patent document 1, as a method for suppressing the viscosity increase rate after the crosslinking agent is blended in the adhesive composition, a method using a reaction inhibitor, a method of adding a solvent for suppressing the viscosity increase, a method using a crosslinking agent for blocking (blocking) a functional group such as blocked isocyanate, and the like are mentioned, but they are not specifically described.
Further, patent document 2 discloses a polyurethane production method using a catalyst system containing: even with the use of a metal acetylacetone catalyst of iron, copper, etc., which is very highly active at low temperatures, metal acetylacetone and acetylacetone which do not cause early curing and have excellent stability and good catalytic activity are used.
However, in the method described in patent document 2, the weight ratio of the metal acetylacetone to the acetylacetone is set to 2:1, but even when this mixing ratio is used in the production process of the acrylic adhesive, the crosslinking reaction cannot be temporarily stopped.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-001440
Patent document 2: japanese patent laid-open No. 2008-285681
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition for a surface protection film of a polarizing plate, which has antistatic performance without using an organic tin compound, has an excellent balance of adhesive force at a low peeling speed and a high peeling speed, and has a long shelf life and excellent durability and reworkability, and a surface protection film.
Means for solving the problems
In order to solve the above problems, the present invention provides an adhesive composition comprising,
the adhesive composition includes: (A) 100 parts by weight of a copolymer of (B) a hydroxyl group-containing copolymerizable monomer as a copolymerizable monomer group and at least one (meth) acrylate monomer having an alkyl group with a carbon number of C4 to C18; (C) 0.1 to 10 parts by weight of a bifunctional or higher isocyanate compound; (D) 0.001-0.5 part by weight of a crosslinking catalyst for the metal chelate; (E) 0.1 to 200 parts by weight of a keto-enol tautomer compound; and 0.05 to 5 parts by weight of an ionic compound having a melting point of 25 to 50 ℃ as an antistatic agent (F), and the ratio of (E)/(D) by weight is 70 to 700.
Further, it is preferable that the hydroxyl group-containing copolymerizable monomer (B) is at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide.
The difunctional or higher isocyanate compound (C) is preferably a compound which is a non-cyclic aliphatic isocyanate compound and is produced by reacting a diisocyanate compound with a diol compound. The diisocyanate compound is an aliphatic diisocyanate, and is preferably one selected from the group consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. The diol compound is preferably one selected from the group consisting of 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-ethyl-2-butyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol monohydroxypivalate, polyethylene glycol, and polypropylene glycol.
Further, as the (C) difunctional or higher isocyanate compound, the trifunctional isocyanate compound is preferably at least one compound selected from the group consisting of an isocyanurate of a hexamethylene diisocyanate compound, an isocyanurate of an isophorone diisocyanate compound, an adduct of a hexamethylene diisocyanate compound, an adduct of an isophorone diisocyanate compound, a biuret of a hexamethylene diisocyanate compound, a biuret of an isophorone diisocyanate compound, an isocyanurate of a toluene diisocyanate compound, an isocyanurate of a xylylene diisocyanate compound, an isocyanurate of a hydrogenated xylylene diisocyanate compound, an adduct of a toluene diisocyanate compound, an adduct of a xylylene diisocyanate compound, and an adduct of a hydrogenated xylylene diisocyanate compound.
The crosslinking catalyst in the binder composition is preferably at least one selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds.
The antistatic agent (F) is preferably an ionic compound having a melting point of 25 to 50 ℃ in an amount of 0.05 to 5.0 parts by weight based on 100 parts by weight of the copolymer, and/or an ionic compound having an acryloyl group in an amount of 0.1 to 5.0% by weight based on 100 parts by weight of the copolymer.
It is preferable that the copolymer includes at least one or more of a carboxyl group-containing monomer, a nitrogen-containing vinyl monomer having no hydroxyl group, and a polyalkylene glycol mono (meth) acrylate monomer as another copolymerizable monomer group, and/or includes a polyether siloxane compound and other conventional antioxidants as additives.
Further, it is preferable that the adhesive layer obtained by crosslinking the adhesive composition has an adhesive strength of 0.05 to 0.1N/25mm at a low peeling speed of 0.3m/min and an adhesive strength of 1.0N/25mm or less at a high peeling speed of 30 m/min.
The surface resistivity of the pressure-sensitive adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition is preferably 9.0X 10+11Omega/□ or less, and the peeling static voltage is + -0-0.5 kV.
The present invention also provides an adhesive film comprising a resin film and an adhesive layer formed on one or both surfaces of the resin film, wherein the adhesive layer is obtained by crosslinking the adhesive composition.
The present invention also provides a surface protective film comprising a resin film and, formed on one surface thereof, an adhesive layer obtained by crosslinking the adhesive composition, wherein the surface protective film is drawn on the resin film with a ballpoint pen through the adhesive layer, and then contamination is not transferred to an adherend.
The surface protective film of the present invention can be used as a surface protective film for a polarizing plate.
In the surface protective film of the present invention, it is preferable that the resin film is subjected to an antistatic and antifouling treatment on the surface thereof opposite to the side on which the adhesive layer is formed.
Effects of the invention
The present invention can satisfy all the performances required for an adhesive layer of a surface protective film, which have not been solved in the prior art, without using an organic tin compound, and can obtain excellent antistatic performance and prevent the adhesive residue phenomenon. Specifically, not only can excellent antistatic performance be maintained, but also the amount of the antistatic agent added can be reduced, and the performance of preventing adhesive residue can be improved.
Detailed Description
The present invention will be described below based on preferred embodiments.
The adhesive composition of the present invention comprises: (A) 100 parts by weight of a copolymer of (B) a hydroxyl group-containing copolymerizable monomer as a copolymerizable monomer group and at least one (meth) acrylate monomer having an alkyl group with a carbon number of C4 to C18; (C) 0.1 to 10 parts by weight of a bifunctional or higher isocyanate compound; (D) 0.001-0.5 part by weight of a crosslinking catalyst for the metal chelate; (E) 0.1 to 200 parts by weight of a keto-enol tautomer compound; and 0.05 to 5 parts by weight of an ionic compound having a melting point of 25 to 50 ℃ as an antistatic agent (F), and the ratio of (E)/(D) by weight is 70 to 700.
The copolymer may include at least one or more of a carboxyl group-containing monomer, a nitrogen-containing vinyl monomer containing no hydroxyl group, and a polyalkylene glycol mono (meth) acrylate monomer as another copolymerizable monomer group.
The antistatic agent (F) may be an ionic compound having a melting point of 25 to 50 ℃ in an amount of 0.05 to 5.0 parts by weight based on 100 parts by weight of the copolymer, and/or an ionic compound having an acryloyl group in an amount of 0.1 to 5.0% by weight based on 100 parts by weight of the copolymer.
The adhesive composition of the present invention may further contain a polyether siloxane compound and other conventional antioxidants as additives.
Examples of the (meth) acrylate monomer having an alkyl group and having from C4 to C18 include: butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, myristyl (meth) acrylate, isotetradecyl (meth) acrylate, dodecyl (meth) acrylate, and the like, Cetyl (meth) acrylate, isocetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and the like.
The content of the (meth) acrylate monomer having an alkyl group and having a carbon number of C4-C18 is preferably 50-98 parts by weight based on 100 parts by weight of the copolymer.
Examples of the (B) hydroxyl group-containing copolymerizable monomer include: hydroxyalkyl (meth) acrylates such as 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate; hydroxyl group-containing (meth) acrylamides such as N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide.
Preferably, the hydroxyl group-containing copolymerizable monomer is at least one member selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide.
The content of the hydroxyl group-containing copolymerizable monomer (B) is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the copolymer.
The copolymer may further include at least one or more of a carboxyl group-containing monomer, a nitrogen-containing vinyl monomer containing no hydroxyl group, and a polyalkylene glycol mono (meth) acrylate monomer as another copolymerizable monomer group.
The carboxyl group-containing monomer is preferably at least one member selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyltetrahydrophthalic acid.
When the aforementioned copolymer includes a carboxyl group-containing monomer as the other copolymerizable monomer group, the content of the carboxyl group-containing monomer is preferably 0.1 to 1.0 part by weight with respect to 100 parts by weight of the aforementioned copolymer. The aforementioned copolymer may not contain the aforementioned carboxyl group-containing monomer.
The polyalkylene glycol mono (meth) acrylate monomer may be any compound as long as one of a plurality of hydroxyl groups of the polyalkylene glycol is esterified to a (meth) acrylate. Since the (meth) acrylate group is a polymerizable group, it can be copolymerized with a copolymer of the main agent. The other hydroxyl group may be in the state of OH, an alkyl ether such as methyl ether or ethyl ether, or a saturated carboxylic acid ester such as acetic ester.
Examples of the alkylene group of the polyalkylene glycol include an ethylene group, a propylene group, and a butylene group, but are not limited thereto. The polyalkylene glycol may be a copolymer of two or more polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol. Examples of the copolymer of polyalkylene glycol include polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, and polyethylene glycol-polypropylene glycol-polybutylene glycol, and the copolymer may be a block copolymer or a random copolymer.
The average number of repetitions of the alkylene oxide constituting the polyalkylene glycol chain in the polyalkylene glycol mono (meth) acrylate monomer is preferably 3 to 14. The "average number of repetitions of alkylene oxide" means the average number of repetitions of alkylene oxide units in the "polyalkylene glycol chain" moiety contained in the molecular structure of the aforementioned polyalkylene glycol mono (meth) acrylate monomer.
The polyalkylene glycol mono (meth) acrylate monomer is preferably at least one selected from the group consisting of polyalkylene glycol mono (meth) acrylate, methoxypolyalkylene glycol (meth) acrylate, and ethoxypolyalkylene glycol (meth) acrylate.
More specifically, there may be mentioned: polyethylene glycol-mono (meth) acrylate, polypropylene glycol-mono (meth) acrylate, polybutylene glycol-mono (meth) acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate, polyethylene glycol-polybutylene glycol-mono (meth) acrylate, polypropylene glycol-polybutylene glycol-mono (meth) acrylate, polyethylene glycol-polypropylene glycol-polybutylene glycol-mono (meth) acrylate; methoxy polyethylene glycol- (meth) acrylate, methoxy polypropylene glycol- (meth) acrylate, methoxy polybutylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polybutylene glycol- (meth) acrylate, methoxy-polypropylene glycol-polybutylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol-polybutylene glycol- (meth) acrylate; ethoxy polyethylene glycol- (meth) acrylate, ethoxy polypropylene glycol- (meth) acrylate, ethoxy polybutylene glycol- (meth) acrylate, ethoxy-polyethylene glycol-polypropylene glycol- (meth) acrylate, ethoxy-polyethylene glycol-polybutylene glycol- (meth) acrylate, ethoxy-polypropylene glycol-polybutylene glycol- (meth) acrylate, ethoxy-polyethylene glycol-polypropylene glycol-polybutylene glycol- (meth) acrylate, and the like.
The content of the polyalkylene glycol mono (meth) acrylate monomer is preferably 0 to 50 parts by weight with respect to 100 parts by weight of the copolymer. The aforementioned copolymer may not contain the aforementioned polyalkylene glycol mono (meth) acrylate monomer.
Examples of the nitrogen-containing vinyl monomer containing no hydroxyl group include: vinyl monomers containing an amide bond, vinyl monomers containing an amino group, vinyl monomers having a nitrogen-containing heterocyclic structure, and the like. More specifically, there may be mentioned: cyclic nitrogen vinyl compounds having an N-vinyl-substituted heterocyclic structure such as N-vinyl-2-pyrrolidone, N-vinylpyrrolidone, methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, and N-vinyllaurolactam; cyclic nitrogen vinyl compounds having an N- (meth) acryloyl-substituted heterocyclic structure such as N- (meth) acryloyl morpholine, N- (meth) acryloyl piperazine, N- (meth) acryloyl aziridine, N- (meth) acryloyl azetidine, N- (meth) acryloyl pyrrolidine, N- (meth) acryloyl piperidine, N- (meth) acryloyl azepane, and N- (meth) acryloyl azocane; cyclic nitrogen vinyl compounds having a heterocyclic structure containing a nitrogen atom and a vinyl-based unsaturated bond in the ring, such as N-cyclohexylmaleimide and N-phenylmaleimide; unsubstituted or monoalkyl-substituted (meth) acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-tert-butyl (meth) acrylamide; dialkyl-substituted (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-dipropylacrylamide, N-diisopropyl (meth) acrylamide, N-dibutyl (meth) acrylamide, N-ethyl-N-methyl (meth) acrylamide, N-methyl-N-propyl (meth) acrylamide, and N-methyl-N-isopropyl (meth) acrylamide; n, N-dimethylaminomethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylate, N-dimethylaminoisopropyl (meth) acrylate, N-dimethylaminobutyl (meth) acrylate, N-diethylaminomethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, N-ethyl-N-methylaminoethyl (meth) acrylate, N-methyl-N-propylaminoethyl (meth) acrylate, N-methyl-N-isopropylaminoethyl (meth) acrylate, N-dibutylaminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, N-dimethylaminoethyl, Dialkylamino (meth) acrylates such as t-butylaminoethyl (meth) acrylate; n, N-dialkyl-substituted aminopropyl (meth) acrylamides such as N, N-dimethylaminopropyl (meth) acrylamide, N-diethylaminopropyl (meth) acrylamide, N-dipropylaminopropyl (meth) acrylamide, N-diisopropylaminopropyl (meth) acrylamide, N-ethyl-N-methylaminopropyl (meth) acrylamide, N-methyl-N-propylaminopropyl (meth) acrylamide, and N-methyl-N-isopropylaminopropyl (meth) acrylamide; n-vinylcarboxylic acid amides such as N-vinylformamide, N-vinylacetamide, and N-vinyl-N-methylacetamide; (meth) acrylamides such as N-methoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, and N, N-methylenebis (meth) acrylamide; unsaturated carboxylic acid nitriles such as (meth) acrylonitrile; and the like.
The content of the nitrogen-containing vinyl monomer having no hydroxyl group is preferably 0 to 20 parts by weight based on 100 parts by weight of the copolymer. The copolymer may not contain the above-mentioned nitrogen-containing vinyl monomer having no hydroxyl group.
The (C) bifunctional or higher isocyanate compound may be at least one or two or more selected from polyisocyanate compounds having at least two or more isocyanate (NCO) groups in one molecule. The polyisocyanate compound includes aliphatic isocyanates, aromatic isocyanates, acyclic isocyanates, alicyclic isocyanates and the like, and any of them can be used in the present invention. Specific examples of the polyisocyanate compound include: aliphatic isocyanate compounds such as Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), and trimethylhexamethylene diisocyanate (TMDI); aromatic isocyanate compounds such as diphenylmethane diisocyanate (MDI), Xylylene Diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI), dimethyldiphenylene diisocyanate (TOID), and Toluene Diisocyanate (TDI).
Examples of the trifunctional or higher isocyanate compound include: a biuret-modified product or an isocyanurate-modified product of a difunctional isocyanate compound (a compound having two NCO groups in one molecule), and an adduct (a polyol-modified product) of a trivalent or higher polyol (a compound having at least three OH groups in one molecule) such as Trimethylolpropane (TMP) or glycerin.
As the (C) difunctional or higher isocyanate compound, only the (C-1) trifunctional isocyanate compound or only the (C-2) difunctional isocyanate compound may be used. Further, (C-1) a trifunctional isocyanate compound and (C-2) a difunctional isocyanate compound may be used in combination.
The (C-1) trifunctional isocyanate compound used in the present invention preferably includes at least one or more selected from the group consisting of (C-1-1) first aliphatic isocyanate compounds, and at least one or more selected from the group consisting of (C-1-2) second aromatic isocyanate compounds, wherein the (C-1-1) first aliphatic isocyanate compounds are composed of isocyanurates of hexamethylene diisocyanate compounds, isocyanurates of isophorone diisocyanate compounds, adducts of hexamethylene diisocyanate compounds, adducts of isophorone diisocyanate compounds, biurets of hexamethylene diisocyanate compounds, and biurets of isophorone diisocyanate compounds; the (C-1-2) second aromatic isocyanate compound group is composed of isocyanurate of tolylene diisocyanate compound, isocyanurate of xylylene diisocyanate compound, isocyanurate of hydrogenated xylylene diisocyanate compound, adduct of tolylene diisocyanate compound, adduct of xylylene diisocyanate compound, and adduct of hydrogenated xylylene diisocyanate compound. It is preferable to use (C-1-1) the first aliphatic isocyanate compound group and (C-1-2) the second aromatic isocyanate compound group in combination. In the present invention, by using at least one or more selected from the group consisting of (C-1-1) first aliphatic isocyanate compounds and at least one or more selected from the group consisting of (C-1-2) second aromatic isocyanate compounds in combination as the (C-1) trifunctional isocyanate compounds, the balance of adhesive strength in the low-speed peeling region and the high-speed peeling region can be further improved.
Further, it is preferable that the (C-1) trifunctional isocyanate compound includes at least one or more selected from the group consisting of the (C-1-1) first aliphatic isocyanate compound and at least one or more selected from the group consisting of the (C-1-2) second aromatic isocyanate compound, and the total content of the (C) trifunctional or more isocyanate compounds is 0.5 to 5.0 parts by weight based on 100 parts by weight of the copolymer. Further, the mixing ratio of at least one or more selected from the group consisting of (C-1-1) first aliphatic isocyanate compounds and at least one or more selected from the group consisting of (C-1-2) second aromatic isocyanate compounds is preferably (C-1-1) to (C-1-2) in the range of 10% to 90% to 10% by weight.
The (C-2) difunctional isocyanate compound used in the present invention is preferably a non-cyclic aliphatic isocyanate compound produced by reacting a diisocyanate compound with a diol compound.
For example, when the general formula "O ═ C ═ N — N ═ C ═ O" (where X is a 2-valent group) represents a diisocyanate compound and the general formula "HO — Y — OH" (where Y is a 2-valent group) represents a diol compound, examples of compounds produced by the reaction between the diisocyanate compound and the diol compound include compounds represented by the following general formula Z.
[ general formula Z ]
O＝C＝N-X-(NH-CO-O-Y-O-CO-NH-X)n-N＝C＝O
Here, n is an integer of 0 or more. When N is 0, formula Z represents "O ═ C ═ N-X-N ═ C ═ O". The difunctional non-cyclic aliphatic isocyanate compound may include a compound of the general formula Z in which n is 0 (a diisocyanate compound which is not reacted with the diol compound), and preferably a compound containing n as an essential component and an integer of 1 or more. The difunctional non-cyclic aliphatic isocyanate compound may also be a mixture of a plurality of compounds of the formula Z in which n is different.
The diisocyanate compound represented by the general formula "O ═ C ═ N — N ═ C ═ O" is an aliphatic diisocyanate. Preferably, X is a non-cyclic aliphatic 2-valent group. The aliphatic diisocyanate is preferably one or more compounds selected from the group consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate.
The diol compound represented by the general formula "HO-Y-OH" is an aliphatic diol. Preferably, Y is a non-cyclic aliphatic 2-valent group. The diol compound is preferably one or more compounds selected from the group consisting of 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-ethyl-2-butyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol monohydroxypivalate, polyethylene glycol, and polypropylene glycol.
The weight ratio (C-1/C-2) of the (C-1) trifunctional isocyanate compound to the (C-2) difunctional isocyanate compound is preferably 1 to 90. The amount of the (C) difunctional or higher isocyanate compound is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the copolymer.
In the case where a polyisocyanate compound is used as the crosslinking agent, (D) the crosslinking catalyst of the metal chelate compound may be any one that functions as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent, and examples thereof include: and amine compounds such as tertiary amines, metal chelates, organic tin compounds, organic lead compounds, and organic zinc compounds. Metal chelates are used as crosslinking catalysts in the present invention.
The metal chelate compound is a compound in which one or more polydentate ligands L are bonded to a central metal atom M. The metal chelate may or may not have one or more monodentate ligands X bonded to the metal atom M. For example, when the metal chelate in which the metal atom M is one is represented by the formula M (L)m(X)nWhen expressed, m is not less than 1, and n is not less than 0. When m is 2 or more, m L's may be the same ligand or different ligands. When n is 2 or more, n X's may be the same ligand or different ligands.
Examples of the metal atom M include Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, and Sn.
Examples of the polydentate ligand L include: beta-keto esters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oil acetoacetate, lauryl acetoacetate, and stearyl acetoacetate; beta-diketones such as acetylacetone (also known as 2, 4-pentanedione), 2, 4-hexanedione, and benzoylacetone. These are keto-enol tautomer compounds, and in the polydentate ligand L, enolates (e.g., acetylacetonates) obtained by deprotonating enols may be used.
Examples of the monodentate ligand X include a halogen atom such as a chlorine atom or a bromine atom, an acyloxy group such as a pentanoyl group, a hexanoyl group, a 2-ethylhexanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, a selenoyl group, or a stearoyl group, and an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, or a butoxy group.
Specific examples of the metal chelate compound include: tris (2,4-pentanedionato) iron (III) (Tris (2,4-pentanedionato) iron (III)), iron triacetylacetonate, titanium triacetylacetonate, ruthenium triacetylacetonate, zinc diacetylacetonate, aluminum triacetylacetonate, zirconium tetraacetoacetonate, Tris (2, 4-hexanedionato) iron (III), zinc bis (2, 4-hexanedionato), titanium Tris (2, 4-hexanedionato), aluminum Tris (2, 4-hexanedionato), zirconium tetrakis (2, 4-hexanedionato), and the like.
As the organotin compound, there may be mentioned: dialkyl tin oxides, fatty acid salts of dialkyl tin, fatty acid salts of stannous, and the like. Conventionally, dibutyltin compounds have been used in many cases, but in recent years, the problem of toxicity of organotin compounds has been pointed out, and particularly tributyltin (TBT) contained in dibutyltin compounds is also concerned as an endocrine interferon. From the viewpoint of safety, long-chain alkyl tin compounds such as dioctyltin compounds are preferred. Specific examples of the organotin compound include dioctyltin oxide and dioctyltin dilaurate. Although a Sn compound may be used temporarily, in view of the trend of requiring a more safe substance in the future, it is preferable to use Al, Ti, F, which are safer than SneAnd the like.
The metal chelate compound in the binder composition of the present invention preferably contains at least one selected from the group consisting of an aluminum chelate compound, a titanium chelate compound and an iron chelate compound.
The content of the crosslinking catalyst of the metal chelate (D) is preferably 0.001 to 0.5 part by weight based on 100 parts by weight of the copolymer.
As (E) keto-enol tautomer compounds, there may be mentioned: beta-keto esters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oil acetoacetate, lauryl acetoacetate, and stearyl acetoacetate; beta-diketones such as acetylacetone, 2, 4-hexanedione, and benzoylacetone. These binder compositions containing a polyisocyanate compound as a crosslinking agent can inhibit excessive increase in viscosity or gelation of the binder composition after the crosslinking agent is blended, and can prolong the pot life of the binder composition, by blocking the isocyanate group of the crosslinking agent.
The content of (E) the keto-enol tautomer compound is preferably 0.1 to 200 parts by weight relative to 100 parts by weight of the copolymer.
In contrast to (D) the crosslinking catalyst of the metal chelate, the (E) keto-enol tautomer compound has an effect of inhibiting crosslinking, and therefore, it is preferable to appropriately set the ratio of the (E) keto-enol tautomer compound to the crosslinking catalyst of the (D) metal chelate. In order to prolong the pot life of the adhesive composition and improve the storage stability, it is preferable that the weight part ratio of the crosslinking catalyst of (E) keto-enol tautomer compound/(D) metal chelate compound (E)/(D) is high. The value of (E)/(D) is preferably in the range of 70 to 700, more preferably 70 to 300, and most preferably 80 to 300.
Examples of the antistatic agent (F) include an antistatic agent contained in the binder composition and an antistatic agent copolymerized in the copolymer. The content of the (F) antistatic agent is preferably 0.05 to 5.0 parts by weight relative to 100 parts by weight of the copolymer.
Preferably, (F) the antistatic agent is (F-1) an ionic compound having a melting point of 25 to 50 ℃ and/or (F-2) an ionic compound containing an acryloyl group.
In the present invention, (F-1) an ionic compound having a melting point of 25 to 50 ℃ is added to the copolymer and/or (F-2) an ionic compound having an acryloyl group is copolymerized to the copolymer as the antistatic agent (F). It is presumed that these (F) antistatic agents have a low melting point and a long-chain alkyl group, and therefore have a high affinity with the acrylic copolymer.
The ionic compound having a melting point of (F-1) of 25 to 50 ℃ is an ionic compound having a cation and an anion, and examples thereof include: the cation is nitrogen-containing onium cation such as pyridinium cation, imidazolium cation, pyrimidinium cation, pyrazolium cation, pyrrolium cation, and ammonium cation, or phosphonium cation and sulfonium cation, and the anion is hexafluorophosphate (PF)6 -) Thiocyanate (SCN)-) Alkyl benzene sulfonate (RC)6H4SO3 -) Perchlorate (ClO)4 -) Tetrafluoroborate (BF)4 -) And bis (fluorosulfonyl) imide (FSI), bis (trifluoromethanesulfonyl) imide (TFSI), Trifluoromethanesulfonate (TF), and the like. Preferably, the compound is solid at room temperature (e.g., 25 ℃) and can have a melting point of 25 to 50 ℃ by selecting the chain length of the alkyl group, the position of the substituent, the number of the substituent, and the like. Preferred cations are quaternary azonium cations, and there may be mentioned: quaternary pyridinium cations such as 1-alkylpyridinium (the carbon atom at the 2-6 position may or may not have a substituent), quaternary imidazolium cations such as 1, 3-dialkylimidazolium (the carbon atom at the 2,4, or 5 position may or may not have a substituent), quaternary ammonium cations such as tetraalkylammonium, and the like.
The content of the (F-1) ionic compound having a melting point of 25 to 50 ℃ is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the copolymer.
The (F-2) acryloyl group-containing ionic compound is an ionic compound having a cation and an anion, and examples thereof include: the cation is (methyl) acryloyloxyalkyltrialkylammonium (R)3N+-CnH2n-OCOCQ＝CH2Wherein Q is H or CH3R ═ alkyl), etc., a (meth) acryloyl group-containing cation; the anion is hexafluorophosphate radical (PF)6 -) Thiocyanate (SCN)-) Organic sulfonic acid Radical (RSO)3 -) Perchlorate (ClO)4 -) Tetrafluoro (tetrafluoro) compoundBorate radical (BF)4 -) And an imide group (R) containing FF 2N-) And the like, inorganic or organic anions. As F-containing imide radical (R)F 2N-) R of (A) to (B)FExamples thereof include a perfluoroalkylsulfonyl group and a fluorosulfonyl group such as a trifluoromethanesulfonyl group and a pentafluoroethanesulfonyl group. Examples of the F-containing imide group include bis (fluorosulfonyl) imide group [ (FSO)2)2N-Bis (trifluoromethanesulfonyl) imide group [ (CF)3SO2)2N-Bis (pentafluoroethanesulfonyl) imide group [ (C)2F5SO2)2N-And the like are described.
The copolymerization amount of the (F-2) acryloyl group-containing ionic compound in the copolymer is preferably 0.1 to 5.0% by weight.
Specific examples of the antistatic agent (F) include, but are not particularly limited to, (F-1) an ionic compound having a melting point of 25 to 50 ℃, and specific examples thereof include 1-octylpyridinium hexafluorophosphate, 1-nonylphenium hexafluorophosphate, 2-methyl-1-dodecylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzene sulfonate, 1-dodecylpyridinium thiocyanate, 1-dodecylpyridinium dodecylbenzene sulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate, quaternary ammonium salts of trifluoromethanesulfonic acid, and the like. Further, specific examples of the (F-2) acryloyl group-containing ionic compound include dimethylaminomethyl (meth) acrylate hexafluorophosphate methyl salt [ (CH-2)3)3N+CH2OCOCQ＝CH2·PF6 -Wherein Q is H or CH3Dimethyl aminoethyl (meth) acrylate bis (trifluoromethanesulfonyl) imide methyl salt [ (CH)3)3N+(CH2)2OCOCQ＝CH2·(CF3SO2)2N-Wherein Q is H or CH3Dimethylaminomethylmethacrylate bis (fluorosulfonyl) imide methyl salt [ (CH ]3)3N+CH2OCOCQ＝CH2·(FSO2)2N－Wherein Q is H or CH3And the like.
The adhesive composition of the present invention may contain a polyether siloxane compound and other conventional antioxidants as additives.
The aforementioned polyether-modified silicone compound is a silicone compound having a polyether group, except for the usual silicone unit (-SiR)1 2-O-) and a siloxane unit (-SiR) comprising a polyether group1(R2O(R3O)nR4) -O-). Herein, R is1Represents one or more alkyl or aryl groups, R2And R3Represents one or more alkylene groups, R4Represents one or two or more kinds of alkyl groups, acyl groups, etc. (terminal groups). Examples of polyether groups include: polyoxyethylene group ((C)2H4O)n) Or polyoxypropylene ((C)3H6O)n) And the like.
Preferably, the polyether-modified silicone compound is a polyether-modified silicone compound having an HLB value of 7 to 15. The content of the polyether-modified siloxane compound is preferably 0.01 to 1.0 part by weight, more preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the copolymer.
The HLB is a hydrophilic-lipophilic balance (ratio of hydrophilicity to lipophilicity) defined in JIS K3211 (surfactant).
The aforementioned polyether-modified siloxane compound can be obtained, for example, by the following method: an organic compound having an unsaturated bond and a polyoxyalkylene group is grafted to the main chain of a polyorganosiloxane having a silane group by a hydrosilylation reaction. Specifically, there may be mentioned: dimethylsiloxane-methyl (polyoxyethylene) siloxane copolymers, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymers, dimethylsiloxane-methyl (polyoxypropylene) siloxane copolymers, and the like.
By blending the polyether-modified siloxane compound with the adhesive composition, the adhesive force and reworking performance of the adhesive can be improved. When the adhesive composition does not contain the polyether-modified siloxane compound, the cost can be made lower.
Examples of the antioxidant include hindered phenol antioxidants, polyphenol compounds, tocopherol compounds, and the like. Among them, a tocopherol compound is preferable. Tocopherols are usually vitamin E, also from natural chemicals. Therefore, the negative influence on human bodies is less, the safety in use is high, and the environment is protected. Further, since it is oil-soluble and liquid at room temperature, it is excellent in compatibility with the binder composition and also excellent in precipitation resistance. The storage stability of the adhesive is improved by blending the tocopherol compound as the antioxidant, and therefore, the pot life of the adhesive composition blended with the curing agent is improved.
The tocopherol compound used in the present invention is preferably a compound having a phenolic hydroxyl group without converting the phenolic hydroxyl group of tocopherol into an ester or the like, from the viewpoint of being used by being blended in a binder composition (not being metabolized as in the human body). Examples thereof include tocopherol and tocotrienol. It is known that there are differences among tocopherols and tocotrienols, including natural compounds (d-form), non-natural compounds (l-form), and racemates of equal-amount mixtures thereof (dl-form). The natural compound (d-form) and the racemic modification (dl-form) are preferred because they can be used as food additives.
Specific tocopherol compounds include compounds selected from the group consisting of d-αTocopherol, dl-αAt least one member selected from the group consisting of-tocopherol, d-beta-tocopherol, dl-beta-tocopherol, d-gamma-tocopherol, dl-gamma-tocopherol, d-beta 2-tocopherol, dl-delta-tocopherol, d-beta 0-tocotrienol, dl-alpha-tocotrienol, d-beta 1-tocotrienol, dl-beta-tocotrienol, d-gamma-tocotrienol, dl-gamma-tocotrienol, d-delta-tocotrienol and dl-delta-tocotrienol. Two or more tocopherol compounds may be used in combination. As food additives, what are called "mixed tocopherols" are d-alpha-tocopherol, d-beta-tocopherol, d-gamma-tocopherol and d-delta-tocopherolA mixture containing tocopherol as a main ingredient; what is called "tocotrienol" is a mixture of d- α -tocotrienol, d- β -tocotrienol, d- γ -tocotrienol and d- δ -tocotrienol as main components.
When the binder composition of the present invention contains a tocopherol compound, the content of the tocopherol compound is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the copolymer.
Further, as other components, known additives such as a copolymerizable (meth) acrylic monomer containing an alkylene oxide (alkylene oxide), a (meth) acrylamide monomer, a dialkyl-substituted acrylamide monomer, a surfactant, a curing catalyst, a plasticizer, a filler, a curing inhibitor, a processing aid, an antioxidant, and an antioxidant can be appropriately blended. These may be used alone or in combination of two or more.
The copolymer as the main agent for the adhesive composition of the present invention can be synthesized by copolymerizing (a) at least one of (meth) acrylate monomers having an alkyl group and a carbon number of C4 to C18 with (B) a hydroxyl group-containing copolymerizable monomer as a copolymerizable monomer group. The method of polymerizing the copolymer is not particularly limited, and an appropriate polymerization method such as solution polymerization or emulsion polymerization can be used.
When (F-2) an acryloyl group-containing ionic compound is used as the antistatic agent (F), the copolymer as the main agent used in the adhesive composition of the present invention can be synthesized by copolymerizing (A) at least one of (meth) acrylate monomers having an alkyl group with a carbon number of C4 to C18, with (B) a hydroxyl group-containing copolymerizable monomer as the copolymerizable monomer group, and (F-2) an acryloyl group-containing ionic compound.
The copolymer may further contain at least one or more of a carboxyl group-containing monomer, a nitrogen-containing vinyl monomer containing no hydroxyl group, and a polyalkylene glycol mono (meth) acrylate monomer as another copolymerizable monomer group.
The adhesive composition of the present invention can be prepared by blending (C) a bifunctional or higher isocyanate compound, (D) a crosslinking catalyst for a metal chelate, (E) a keto-enol tautomer compound, (F-1) an ionic compound having a melting point of 25 to 50 ℃ as an antistatic agent (F), and further an appropriate optional additive into the copolymer. When (F-2) the ionic compound having an acryloyl group is polymerized in the main copolymer, the copolymer may be further added with an ionic compound having a melting point of (F-1) of 25 to 50 ℃ as (F) the antistatic agent, or without an ionic compound having a melting point of (F-1) of 25 to 50 ℃ as (F) the antistatic agent.
The copolymer is preferably an acrylic polymer, and preferably contains 50 to 100 wt% of a (meth) acrylate monomer or an acrylic monomer such as (meth) acrylic acid or (meth) acrylamides.
Further, the acid value of the copolymer is preferably 0.01 to 8.0. This improves the staining property and improves the performance of preventing the adhesive residue phenomenon.
Here, the "acid value" is one of the indexes indicating the acid content, and is expressed in mg of potassium hydroxide required for neutralizing 1g of a carboxyl group-containing polymer.
Preferably, the adhesive layer obtained by crosslinking the adhesive composition has an adhesive strength of 0.05 to 0.1N/25mm at a low peeling speed of 0.3m/min and an adhesive strength of 1.0N/25mm or less at a high peeling speed of 30 m/min. This makes it possible to obtain a performance that the change of the adhesive force with the peeling speed is small, and to peel off quickly even in the case of high-speed peeling. Further, even when the surface protective film is temporarily peeled off for re-attachment, the surface protective film can be easily peeled off from the adherend without requiring an excessive force.
The surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is preferably 9.0X 10+11Omega/□ or less, and the peeling static voltage is + -0-0.5 kV. In the present invention, "+/-0 to 0.5 kV" means "0 to-0.5 kV" and "0 to +0.5 kV", that is, "-0.5 to +0.5 kV". If the surface resistivity is high, the performance of releasing static electricity generated by electrification at the time of peeling is poor, and therefore, by making the surface resistivity sufficiently low, static electricity generated accompanying peeling of the adhesive layer from the adherend can be reducedThe generated peeling static voltage can inhibit the influence on an electric control circuit of the adherend.
The gel fraction of the binder layer (crosslinked binder) obtained by crosslinking the binder composition of the present invention is preferably 95 to 100%. Since the gel fraction is so high, the adhesive force does not become excessively large at a low peeling rate, and the elution of unpolymerized monomers or oligomers from the copolymer is reduced, whereby the reworkability and the durability under high temperature/high humidity conditions can be improved, and the contamination of the adherend can be suppressed.
The adhesive film of the present invention is obtained by forming an adhesive layer on one side or both sides of a resin film, wherein the adhesive layer is obtained by crosslinking the adhesive composition of the present invention. The surface protective film of the present invention is obtained by forming an adhesive layer on one surface of a resin film, wherein the adhesive layer is obtained by crosslinking the adhesive composition of the present invention. The adhesive composition of the present invention has excellent antistatic properties due to the components (a) to (F) blended in a good balance, excellent balance of adhesive strength at low and high peeling speeds, and excellent durability and reworkability (no transfer of contamination to an adherend after drawing on a surface protective film with an adhesive layer interposed therebetween with a ball-point pen). Therefore, it can be preferably used for the surface protective film of a polarizing plate.
In the adhesive film and the surface protective film of the present invention, a polyester film or the like can be used as a base material of a resin film or a release film (separator) for protecting an adhesive layer.
The resin film may be subjected to an anti-fouling treatment with a silicone-based or fluorine-based release agent, a coating agent, silica fine particles, or the like on the surface of the resin film opposite to the side on which the adhesive layer is formed, or may be subjected to an antistatic treatment by coating or mixing with an antistatic agent.
The release film is subjected to a release treatment with a silicone-based or fluorine-based release agent or the like on the surface on the side of being bonded to the adhesive surface of the adhesive layer.
Examples
The present invention will be specifically described below based on examples.
< production of acrylic copolymer >
[ example 1]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, thereby replacing the air in the reaction apparatus with nitrogen gas. Then, 100 parts by weight of 2-ethylhexyl acrylate and 3.5 parts by weight of 8-hydroxyoctyl acrylate were added to the reaction apparatus. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and reacted at 65 ℃ for 6 hours to obtain an acrylic copolymer solution 1 having a weight average molecular weight of 50 ten thousand used in example 1. A part of the acrylic copolymer was taken out and used as a sample for measuring an acid value described later.
Examples 2 to 6 and comparative examples 1 to 3
Acrylic copolymer solutions used in examples 2 to 6 and comparative examples 1 to 3 were obtained in the same manner as the acrylic copolymer solution 1 used in example 1, except that the respective monomer compositions were adjusted as described in (a), (B), (I) and (F-2) in table 1.
TABLE 1
Figure BDA0001663564540000191
< production of adhesive composition and surface protective film >
[ example 1]
1.5 parts by weight of 1-octylpyridinium hexafluorophosphate and 4.0 parts by weight of acetylacetone were added to and stirred with the acrylic copolymer solution 1 of example 1 prepared as described above, and then 1.5 parts by weight of Coronate HX (コロネート HX, isocyanurate of hexamethylene diisocyanate compound) and 0.05 part by weight of tris (2, 4-pentanedionate) iron (III) were added and stirred and mixed to obtain an adhesive composition of example 1. The adhesive composition was applied to a release film composed of a polyethylene terephthalate (PET) film coated with a silicone resin, and then dried at 90 ℃ to remove the solvent, to obtain an adhesive sheet having an adhesive layer thickness of 25 μm.
Then, a polyethylene terephthalate (PET) film having one surface subjected to the antistatic treatment and the antifouling treatment was prepared, and the adhesive sheet was transferred to the surface of the polyethylene terephthalate (PET) film opposite to the surface subjected to the antistatic treatment and the antifouling treatment, to obtain the surface protective film of example 1 having a laminated structure of "PET film subjected to the antistatic treatment and the antifouling treatment/adhesive layer/release film (PET film coated with silicone resin)".
Examples 2 to 6 and comparative examples 1 to 3
Surface protective films of examples 2 to 6 and comparative examples 1 to 3 were obtained in the same manner as the surface protective film of example 1, except that the compositions of the respective additives were adjusted as described in (C) to (F) and (J) of table 2.
TABLE 2
Figure BDA0001663564540000201
Tables 1 and 2 are tables in which the entire table showing the blending ratios of the respective components is divided into two parts, and each of the numerical values in parentheses indicates the numerical value of the weight part of each component obtained by setting the total amount of the group (A) to 100 weight parts. In addition, the ratio of (E)/(D) is shown in table 3. In addition, compound names corresponding to abbreviations of the respective components used in tables 1 and 2 are shown in tables 4 and 5. Furthermore, Coronate (コロネート, registered trademark) HX, Coronate HL, and Coronate L are trade names of japan Polyurethane Industry co (Nippon Polyurethane Industry co., Ltd.), Takenate (タケネート, registered trademark) D-140N, D-127N, D-110N is a trade name of mitsui chemical co., and Desmodur (デスモジュール, registered trademark) N3400 is a trade name of Sumika Bayer Urethane co., Ltd. (resident バイエルウレタン co.).
In Table 1, (F-2) the acryloyl group-containing ionic compound copolymerized in the copolymer and (F) the antistatic agent added after the polymerization, of the antistatic agents (F), are shown in different columns, respectively. TABLE 3
(E)/(D)
Example 1 80
Example 2 85
Example 3 267
Example 4 120
Example 5 333
Example 6 500
Comparative example 1 -
Comparative example 2 12
Comparative example 3 3
TABLE 4
Figure BDA0001663564540000211
TABLE 5
Figure BDA0001663564540000221
< Synthesis of difunctional isocyanate Compound >
The difunctional isocyanate compounds of Synthesis examples 1 and 2 were synthesized by the following method. That is, as shown in tables 6 and 7, diisocyanate and diol compound were mixed at a molar ratio NCO/OH of 16, reacted at 120 ℃ for 3 hours, and then unreacted diisocyanate was removed under reduced pressure using a thin film evaporator to obtain the desired difunctional isocyanate compound.
TABLE 6
Synthesis example 1G-1 Synthesis example 2G-2
Diisocyanate compound HDI HDI
Diol compound H-1 H-2
TABLE 7
Figure BDA0001663564540000231
< test methods and evaluations >
The surface protective films of examples 1 to 6 and comparative examples 1 to 3 were aged for 7 days at 23 ℃ and 50% RH, and then the release film (silicone resin-coated PET film) was peeled off to expose the adhesive layer, thereby obtaining a sample for measuring surface resistivity.
The surface protective film with the exposed adhesive layer was bonded to the surface of the polarizing plate attached to the liquid crystal cell via the adhesive layer, left to stand for 1 day, and then autoclaved at 50 ℃ under 5 atmospheres for 20 minutes, and further left to stand at room temperature for 12 hours, and then used as a sample for measuring the adhesion, the peel static voltage, the reworkability, and the durability.
< adhesion >
The measurement sample (sample obtained by bonding a 25mm wide surface protective film to the surface of a polarizing plate) obtained above was peeled in a 180 ° direction at a low peeling speed (0.3m/min) and a high peeling speed (30m/min) using a tensile tester, and the peel strength was measured and used as the adhesive strength.
< surface resistivity >
After aging and before bonding to the polarizing plate, the release film (silicone resin-coated PET film) was peeled off to expose the adhesive layer, and the surface resistivity of the adhesive layer was measured by using a resistivity meter HirestaUP-HT450(ハイレスタ UP-HT450, manufactured by Mitsubishi Chemical Analytech co., Ltd.).
< peeling Electrostatic Voltage >
The voltage (electrostatic voltage) generated by charging the polarizing plate when the measurement sample obtained above was peeled at 180 ℃ at a tensile speed of 30m/min was measured using high-precision electrostatic sensors SK-035 and SK-200 (manufactured by Keyence Corporation), and the maximum value of the measurement values was defined as the peeling electrostatic voltage.
< reworkability >
After drawing (load 500g, 3 times back and forth) on the surface protective film of the measurement sample obtained above with a ball-point pen, the surface protective film was peeled off from the polarizing plate, and the surface of the polarizing plate was observed to confirm whether or not contamination was transferred to the polarizing plate. Evaluation target criteria: evaluated as "o" when no contamination was transferred to the polarizing plate; "Δ" when it was confirmed that the contamination was at least partially transferred along the trace drawn by the ball-point pen; evaluation was "x" when contamination transfer was confirmed along the trace drawn by the ball-point pen and detachment of the adhesive from the adhesive surface was also confirmed.
< storage period >
The viscosity η of the adhesive composition was measured immediately after blending the additives (C) to (F) and (J)0(initial viscosity), and the viscosity η of the adhesive composition was measured after the adhesive composition was left to stand in a sealed state at 23 ℃ for 8 hours1(viscosity after 8 hours). As an index of the pot life, the term η0Eta at 1.01Value of (i), i.e. eta1/η0The ratio of. The evaluation target criteria are as follows: the viscosity after 8 hours was evaluated as "good" when it was lower than 1.25 times the initial viscosity, as "Δ" when it was 1.25 times or more and lower than 1.50 times, and as "x" when it was 1.50 times or more or gelled after standing for 8 hours.
< durability >
After the measurement sample obtained above was left to stand at 60 ℃ and 90% RH for 250 hours, it was taken out and left to stand at room temperature for further 12 hours, and then the adhesion was measured to confirm whether or not there was a significant increase in the initial adhesion. Evaluation target criteria: when the adhesion force after the test was 1.5 times or less the initial adhesion force, the evaluation was "o", and when it exceeded 1.5 times, the evaluation was "x".
The evaluation results are shown in table 8. In addition, in the surface resistivity, "m × 10" is represented by "mE + n+n"(where m is any real number and n is a positive integer).
TABLE 8
Figure BDA0001663564540000251
The surface protective films of examples 1 to 6 had an adhesive force of 0.05 to 0.1N/25mm at a low peeling speed of 0.3m/min and an adhesive force of 1.0N/25mm or less at a high peeling speed of 30 m/min; surface resistivity of 9.0 × 10+11Below omega/□, the stripping electrostatic voltage is +/-0-0.5 kV; further, after the surface protective film was drawn with a ballpoint pen through an adhesive layer, the transfer of contamination to an adherend was avoided, the pot life was long, and the durability after the ball pen was left to stand in an environment of 60 ℃ and 90% RH for 250 hours was also excellent.
Namely, it has excellent antistatic properties, is excellent in balance of adhesive force at low peeling speed and high peeling speed, and is also excellent in shelf life, durability and reworkability.
In addition, the surface protective films of examples 1 to 6 were highly safe because the adhesive composition did not contain an organotin compound.
The surface protective film of comparative example 1, which does not contain (C) a bifunctional or more isocyanate compound as a crosslinking agent, has an excessively large adhesive force at a low peeling speed of 0.3m/min and a high peeling speed of 30m/min, a high surface resistivity and peeling static electricity, and poor reworkability and durability.
The surface protective film of comparative example 2 was likely to have high peeling static voltage, short pot life, and poor durability due to the small proportion of the (E) keto-enol tautomer compound relative to the (D) metal chelate crosslinking catalyst.
The surface protective film of comparative example 3 may not be coated because the pot life is too short because the proportion of the (E) keto-enol tautomer compound to the (D) metal chelate crosslinking catalyst is small, and crosslinking is performed before coating.
Thus, the surface protective films of comparative examples 1 to 3 could not satisfy all the performance requirements of excellent antistatic performance, excellent balance of adhesive force at low and high peeling speeds, long shelf life, and excellent durability and reworkability.

Claims (9)

1. An adhesive composition characterized by comprising the following components in the following proportions:
100 parts by weight of a copolymer obtained by copolymerizing (A) at least one of (meth) acrylate monomers having an alkyl group and having from C4 to C18 with (B) a hydroxyl group-containing copolymerizable monomer as a copolymerizable monomer group, the copolymer being obtained by copolymerizing a carboxyl group-containing monomer, a polyalkylene glycol mono (meth) acrylate monomer and a hydroxyl group-free nitrogen-containing vinyl monomer;
(C) 0.1 to 10 parts by weight of a bifunctional or higher isocyanate compound;
(D) 0.001-0.5 part by weight of a crosslinking catalyst for the metal chelate;
(E) 4.0 × 100/103.5-200 parts by weight of a keto-enol tautomer compound; and
0.05 to 5 parts by weight of an ionic compound having a melting point of 25 to 50 ℃ as an antistatic agent (F),
and the ratio (E)/(D) by weight of the (E) keto-enol tautomer compound/the (D) metal chelate crosslinking catalyst is 80 to 300,
the crosslinking catalyst of the metal chelate (D) is at least one selected from the group consisting of aluminum chelate, titanium chelate and iron chelate,
the hydroxyl group-containing copolymerizable monomer (B) is contained in a total amount of 0.1 to 10 parts by weight based on 100 parts by weight of the copolymer,
the (F) antistatic agent is at least one ionic compound having a melting point of 25 to 50 ℃ selected from the group consisting of 1-octylpyridinium hexafluorophosphate, 1-nonylpheninium hexafluorophosphate, 2-methyl-1-dodecylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzene sulfonate, 1-dodecylpyridinium thiocyanate, 1-dodecylpyridinium dodecylbenzene sulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate, and quaternary ammonium salt of trifluoromethanesulfonic acid,
the adhesive composition further comprises a tocopherol compound as an antioxidant, the tocopherol compound being at least one selected from the group consisting of d-alpha-tocopherol, dl-alpha-tocopherol, d-beta-tocopherol, dl-beta-tocopherol, d-gamma-tocopherol, dl-gamma-tocopherol, d-delta-tocopherol, dl-delta-tocopherol, d-alpha-tocotrienol, dl-alpha-tocotrienol, d-beta-tocotrienol, dl-beta-tocotrienol, d-gamma-tocotrienol, dl-gamma-tocotrienol, d-delta-tocotrienol, and dl-delta-tocotrienol, and the adhesive composition does not contain a polyether modified siloxane compound.
2. The adhesive composition according to claim 1, wherein the (B) hydroxyl group-containing copolymerizable monomer is at least one member selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide,
the total amount of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate in the hydroxyl group-containing copolymerizable monomer (B) is 0.1 to 3.5X 100/103.5 parts by weight based on 100 parts by weight of the copolymer.
3. The adhesive composition according to claim 1 or 2, wherein,
for the (C) difunctional or higher isocyanate compound,
the difunctional isocyanate compound is a compound which is a non-cyclic aliphatic isocyanate compound and is produced by reacting a diisocyanate compound with a diol compound;
the diisocyanate compound is aliphatic diisocyanate which is one selected from the group consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate,
the diol compound is one selected from the group consisting of 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-ethyl-2-butyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol monohydroxypivalate, polyethylene glycol, and polypropylene glycol,
the trifunctional isocyanate compound is an isocyanurate of a hexamethylene diisocyanate compound, an isocyanurate of an isophorone diisocyanate compound, an adduct of a hexamethylene diisocyanate compound, an adduct of an isophorone diisocyanate compound, a biuret of a hexamethylene diisocyanate compound, a biuret of an isophorone diisocyanate compound, an isocyanurate of a toluene diisocyanate compound, an isocyanurate of a xylylene diisocyanate compound, an isocyanurate of a hydrogenated xylylene diisocyanate compound, an adduct of a toluene diisocyanate compound, an adduct of a xylylene diisocyanate compound, an adduct of a hydrogenated xylylene diisocyanate compound.
4. The adhesive composition according to claim 1 or 2, wherein the adhesive layer obtained by crosslinking the adhesive composition has an adhesive strength of 0.05 to 0.1N/25mm at a low peeling speed of 0.3m/min and an adhesive strength of 1.0N/25mm or less at a high peeling speed of 30 m/min.
5. The adhesive composition according to claim 1 or 2, wherein the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is 9.0 x 10+11Omega/□ or less, and the peeling static voltage is + -0-0.5 kV.
6. An adhesive film comprising a resin film and an adhesive layer formed on one or both surfaces of the resin film, wherein the adhesive layer is obtained by crosslinking the adhesive composition according to any one of claims 1 to 5.
7. A surface protective film comprising a resin film and an adhesive layer formed on one surface of the resin film, wherein the adhesive layer is formed by crosslinking the adhesive composition according to any one of claims 1 to 5, and wherein no stain is transferred to an adherend after drawing on the surface protective film with a ballpoint pen through the adhesive layer.
8. The surface protective film according to claim 7, which is used as a surface protective film for a polarizing plate.
9. The surface protective film according to claim 8, wherein an antistatic and antifouling treatment is performed on a surface of the resin film opposite to a side on which the adhesive layer is formed.
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Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6701727B2 (en) * 2015-12-25 2020-05-27 三菱ケミカル株式会社 Adhesive composition, adhesive obtained by crosslinking this, adhesive for masking film, adhesive for heat resistant adhesive film, heat resistant adhesive film for masking
JP6566568B2 (en) * 2016-02-29 2019-08-28 藤森工業株式会社 Method for producing antistatic surface protective film
JP6521896B2 (en) * 2016-04-25 2019-05-29 藤森工業株式会社 Pressure sensitive adhesive composition and antistatic surface protective film
JP6521906B2 (en) * 2016-06-16 2019-05-29 藤森工業株式会社 Pressure sensitive adhesive composition and antistatic surface protective film
CN106189901B (en) * 2016-07-13 2021-09-28 永大（中山）有限公司 Single-sided pressure-sensitive adhesive tape for packaging, fixing and protecting automobile glass and preparation method thereof
JP6856394B2 (en) * 2017-02-03 2021-04-07 日東電工株式会社 Adhesive composition, adhesive layer, surface protective film, and optical member
JP6677673B2 (en) * 2017-05-15 2020-04-08 藤森工業株式会社 Pressure-sensitive adhesive composition and surface protective film
JP2019143078A (en) * 2018-02-22 2019-08-29 三菱ケミカル株式会社 Pressure sensitive adhesive composition, pressure sensitive adhesive obtained by crosslinking the same, pressure sensitive adhesive for masking film, masking film, self-adhesive film for step of forming transparent electrode layer, tape for step of producing semiconductor, method for using masking film
JP6580759B2 (en) * 2018-07-03 2019-09-25 藤森工業株式会社 Surface protection film
JP6703167B2 (en) * 2019-04-22 2020-06-03 藤森工業株式会社 Adhesive composition and antistatic surface protective film
JP6926274B2 (en) * 2019-04-22 2021-08-25 藤森工業株式会社 Adhesive layer and antistatic surface protective film
JP7328418B2 (en) * 2020-05-07 2023-08-16 藤森工業株式会社 Adhesive film and antistatic surface protection film
JP7132407B2 (en) * 2020-05-07 2022-09-06 藤森工業株式会社 adhesive film
JP6925487B2 (en) * 2020-05-07 2021-08-25 藤森工業株式会社 Adhesive layer and antistatic surface protective film
JP7090755B2 (en) * 2021-01-05 2022-06-24 藤森工業株式会社 Adhesive composition and antistatic surface protective film
KR102395516B1 (en) * 2021-01-29 2022-05-10 율촌화학 주식회사 Acryl-based adhesive compostion and surface protective film for cover glass comprising the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103173165A (en) * 2011-12-20 2013-06-26 日东电工株式会社 Pressure-sensitive adhesive compositions, pressure-sensitive adhesive layers, and pressure-sensitive adhesive sheets
JP2013216738A (en) * 2012-04-05 2013-10-24 Fujimori Kogyo Co Ltd Pressure-sensitive adhesive composition and surface protective film
CN103509502A (en) * 2012-06-20 2014-01-15 藤森工业株式会社 Adhesive composition and surface-protective film

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5733945A (en) 1995-07-20 1998-03-31 Rogers Corporation Process for manufacturing polyurethane using a metal acetyl acetonate/acetyl acetone catalyst system and the product made therefrom
JP2001240830A (en) * 2000-02-28 2001-09-04 Saiden Chemical Industry Co Ltd Adhesive composition and surface protective film
JP2003073638A (en) * 2001-08-31 2003-03-12 Nippon Synthetic Chem Ind Co Ltd:The Self-adhesive composition
JP4149473B2 (en) * 2005-09-21 2008-09-10 サイデン化学株式会社 Polymer composition for pressure-sensitive adhesive, pressure-sensitive adhesive composition for surface protective film, and surface protective film
JP5091434B2 (en) * 2006-07-04 2012-12-05 日本カーバイド工業株式会社 Pressure-sensitive adhesive composition and optical member surface protective film
JP2011001440A (en) 2009-06-18 2011-01-06 Toagosei Co Ltd Adhesive composition
JP5484035B2 (en) * 2009-12-22 2014-05-07 日本カーバイド工業株式会社 Adhesive composition and optical film
JP5770607B2 (en) 2011-11-21 2015-08-26 藤森工業株式会社 Adhesive composition and surface protective film
JP5879160B2 (en) * 2012-03-06 2016-03-08 藤森工業株式会社 Adhesive composition and surface protective film
JP2014015004A (en) * 2012-07-10 2014-01-30 Nitto Denko Corp Release material, method for producing the same and adhesive tape
JP6268407B2 (en) * 2012-07-27 2018-01-31 藤森工業株式会社 Adhesive composition and surface protective film
CN105008482A (en) * 2013-11-15 2015-10-28 Lg化学株式会社 Adhesive composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103173165A (en) * 2011-12-20 2013-06-26 日东电工株式会社 Pressure-sensitive adhesive compositions, pressure-sensitive adhesive layers, and pressure-sensitive adhesive sheets
JP2013216738A (en) * 2012-04-05 2013-10-24 Fujimori Kogyo Co Ltd Pressure-sensitive adhesive composition and surface protective film
CN103509502A (en) * 2012-06-20 2014-01-15 藤森工业株式会社 Adhesive composition and surface-protective film

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