CN108300365B - Adhesive composition, adhesive film and surface protective film - Google Patents
Adhesive composition, adhesive film and surface protective film Download PDFInfo
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- CN108300365B CN108300365B CN201710881073.XA CN201710881073A CN108300365B CN 108300365 B CN108300365 B CN 108300365B CN 201710881073 A CN201710881073 A CN 201710881073A CN 108300365 B CN108300365 B CN 108300365B
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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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
Abstract
A surface protective film comprising a resin film and, formed on one or both surfaces thereof, an adhesive layer obtained by crosslinking an adhesive composition comprising an acrylic polymer, a crosslinking agent and an antistatic agent, the acrylic polymer comprises an alkyl (meth) acrylate having an alkyl group with 4 to 10 carbon atoms as a main component, and is composed of a copolymer obtained by copolymerizing 85 to 99.5 parts by weight of an alkyl (meth) acrylate as the main component and 5 to 15 parts by weight of a copolymerizable monomer containing a hydroxyl group, based on 100 parts by weight of the acrylic polymer, the adhesive composition contains 0.1-5 parts by weight of the cross-linking agent, wherein the cross-linking agent is an isocyanate compound with more than three functions, the antistatic agent is an ionic compound which has a melting point of 30-50 ℃ and is solid at a temperature of 30 ℃.
Description
The present application is a divisional application of applications entitled "adhesive composition, adhesive film, and surface protective film" having application date of 11/2013 and application number of 201310556382.1.
Technical Field
The invention provides an adhesive composition with antistatic performance, an adhesive film and a surface protective film, wherein the adhesive film is formed by forming an adhesive layer with antistatic performance on at least one surface of a resin film by using the adhesive composition.
In addition, the present invention relates to a surface protective film used in a manufacturing process of a liquid crystal display. More particularly, the present invention relates to an adhesive composition for a surface protective film to be adhered to a surface of an optical member such as a polarizing plate, a retardation plate, or an antireflection film constituting a liquid crystal display, and a surface protective film using the adhesive composition.
The adhesive film and the surface protective film of the present invention have particularly excellent antistatic properties. Therefore, it is applied to the surface of an optical film such as a polarizing plate, a retardation plate, and an antireflection film, which are constituent members of a plastic film that is likely to generate static electricity, to protect the surface.
Background
Conventionally, in a process for producing an optical member such as a polarizing plate, a retardation plate, and an antireflection film, which are members constituting a liquid crystal display, a surface protection film for temporary protection is attached to a surface of the optical member. Such a surface protective film is used only in a process of manufacturing an optical member, and is peeled and removed from the optical member when the optical member is inserted into a liquid crystal display. Such a surface protective film for protecting the surface of an optical member is generally also called a "process film" because it is used only in the production process.
The surface protective film used in the process of producing an optical member as described above has an adhesive layer formed on one surface of a polyethylene terephthalate (PET) resin film having optical transparency. A release film subjected to a release treatment for protecting the adhesive layer is bonded to the adhesive layer until the optical member is bonded thereto.
Further, since product tests associated with optical evaluations such as display capability, color tone, contrast, and contamination of impurities of a liquid crystal display panel are performed on optical members such as a polarizing plate, a retardation plate, and an antireflection film in a state where a surface protection film is attached, it is required that the adhesive layer is free from bubbles and impurities as performance requirements for the surface protection film.
In recent years, when a surface protective film is peeled from an optical member such as a polarizing plate, a retardation plate, or an antireflection film, peeling static electricity generated by static electricity generated when an adhesive layer is peeled from an adherend may affect a failure of an electric control circuit of a liquid crystal display.
When a surface protective film is adhered to an optical member such as a polarizing plate, a retardation plate, or an antireflection film, the surface protective film may be temporarily peeled off and then re-attached again for various reasons. In this case, the surface protective film is required to have a property (reworkability) that the surface protective film can be easily peeled off from the optical member to be adhered. In this case, the adhesive layer of the surface protective film is required not to contaminate the adherend, i.e., not to cause a phenomenon called adhesive residue.
In addition, when the surface protective film is peeled from the final optical member such as a polarizing plate, a retardation plate, an antireflection film, or the like, it is required to be quickly peeled. That is, the change in the adhesive force due to the peeling speed is required to be small so as to enable quick peeling even in the case of high-speed peeling.
As described above, in recent years, from the viewpoint of ease of handling when a surface protective film is used, the adhesive layer constituting the surface protective film is required to have the following properties: (1) the balance of the adhesive force is obtained at the peeling speed of the low-speed area and the high-speed area; (2) preventing the occurrence of adhesive residue; (3) the antistatic performance is excellent; and (4) has ReWork (ReWork) properties.
However, even if the performance requirements for the adhesive layer constituting the surface protective film can be individually satisfied, that is, even if the individual performance requirements of (1) to (4) described above can be individually satisfied, it is a very difficult problem to simultaneously satisfy all the performance requirements (1) to (4) that the adhesive layer of the surface protective film is required to have.
In the present specification, the "low speed region" means a region where the peeling speed is in the vicinity of 0.3 m/min; the "high speed region" means a region where the peeling speed is in the vicinity of 30 m/min.
For example, the following proposals are known for (1) achieving a balance of adhesive strength at peeling speeds in a low-speed region and a high-speed region, and (2) preventing the occurrence of adhesive residue.
In an acrylic adhesive layer comprising a copolymer of an alkyl (meth) acrylate having an alkyl group of 7 or less carbon atoms and a copolymerizable compound having a carboxyl group as a main component and crosslinking the copolymer with a crosslinking agent, there is a problem that the adhesive moves to the adherend side and adheres to the adherend when adhered for a long period of time, and the adhesive strength to the adherend is greatly increased with time. In order to avoid this problem, a technique is known in which an adhesive layer is provided by using a copolymer of an alkyl (meth) acrylate having an alkyl group with 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group and crosslinking the copolymer with a crosslinking agent (patent document 1).
In addition, there has been proposed a method of providing an adhesive layer obtained by blending a small amount of a copolymer of an alkyl (meth) acrylate and a copolymerizable compound having a carboxyl group in the same copolymer as described above and crosslinking the blend with a crosslinking agent. However, when the resin composition is used for surface protection of a plastic plate or the like having a low surface tension and a smooth surface, there are problems that a peeling phenomenon such as separation occurs due to heating at the time of processing or storage, and that removability is poor at the time of high-speed peeling in the field of manual handling.
In order to solve these problems, an adhesive composition is proposed which is: an adhesive composition comprising a) 100 parts by weight of an alkyl (meth) acrylate containing an alkyl group having 8 to 10 carbon atoms as a main component, a copolymer of a monomer mixture obtained by adding b)1 to 15 parts by weight of a copolymerizable compound containing a carboxyl group and c)3 to 100 parts by weight of a vinyl ester of an aliphatic carboxylic acid having 1 to 5 carbon atoms, and a crosslinking agent having an equivalent or more of the carboxyl group of the component b) to the copolymer (patent document 2).
The adhesive composition described in patent document 2 is excellent in removability because it does not cause a peeling phenomenon such as separation during processing or storage, and the adhesive strength is not greatly increased with time. Further, even when the film is stored for a long period of time, particularly in a high-temperature environment, the film can be peeled off again with a small force, and at this time, the adhesive does not remain on the adherend, and the film can be peeled off again with a small force even when the film is peeled off at a high speed.
In addition, as a method for imparting antistatic properties to the surface protective film with respect to the excellent antistatic properties of (3), a method of mixing an antistatic agent into the base film has been proposed. Examples of the antistatic agent include (a) various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and a primary to tertiary amino group; (b) an anionic antistatic agent having an anionic group such as a sulfonic acid base, a sulfate ester base, a phosphate ester base, or a phosphonic acid base; (c) amphoteric antistatic agents such as amino acids and amino sulfates; (d) nonionic antistatic agents such as aminoalcohols, glycerols, and polyethylene glycols; (e) a polymer type antistatic agent obtained by polymerizing the above antistatic agent to a high molecular weight (patent document 3).
In recent years, it has been proposed to include such an antistatic agent directly in the adhesive layer, instead of in the base film or to coat the surface of the base film.
In addition, regarding (4) reworkability, for example, there is proposed a binder composition which is: the acrylic resin composition is obtained by blending 0.0001 to 10 parts by weight of a curing agent for an isocyanate compound and a specific silicate oligomer per 100 parts by weight of an acrylic resin (patent document 4).
Patent document 4 describes: the resin composition may contain, as a main monomer component, an alkyl acrylate having an alkyl group of about 2 to 12 carbon atoms, an alkyl methacrylate having an alkyl group of about 4 to 12 carbon atoms, or the like, and may contain a monomer component having another functional group such as a carboxyl group-containing monomer. In general, the main monomer is preferably contained in an amount of 50% by weight or more, and the content of the functional group-containing monomer component is desirably 0.001 to 50% by weight, preferably 0.001 to 25% by weight, and more preferably 0.01 to 25% by weight. The adhesive composition described in patent document 4 has reworkability because changes in cohesive strength and adhesive strength with time are small even at high temperatures or high temperatures and high humidity, and the adhesive strength to a curved surface is excellent.
In general, when the adhesive layer is soft, adhesive residue is likely to occur, and the reworkability is also likely to decrease. That is, peeling is difficult after misapplication, and re-application is difficult. From this viewpoint, in order to impart reworkability, it is necessary to crosslink a monomer having a functional group such as a carboxyl group to the base compound so that the adhesive layer has a certain hardness.
In the prior art, the adhesive layer constituting the surface protective film is required to have the following properties: the balance of the adhesive force is obtained at the peeling speed of the low-speed area and the high-speed area; the antistatic performance is excellent; and has reworkability. However, even if the performance requirements of the individual items (1) to (4) described above can be satisfied, the performance requirements of all of (1) to (4) required for the adhesive layer of the surface protective film cannot be satisfied.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 63-225677;
patent document 2: japanese patent laid-open publication No. 11-256111;
patent document 3: japanese patent laid-open publication No. 11-070629;
patent document 4: japanese patent laid-open No. 8-199130.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition, an adhesive film, and a surface protective film which have excellent antistatic performance, are excellent in balance of adhesive force at peeling speeds in a low speed region and a high speed region, and are also excellent in durability and reworkability.
In order to solve the above problems, the present invention provides an adhesive composition containing an antistatic agent, wherein,
the adhesive composition comprises an acrylic polymer containing an alkyl (meth) acrylate having an alkyl group with 4-10 carbon atoms as a main component,
the acrylic polymer contains 85 to 99.5 parts by weight of the alkyl (meth) acrylate as the main component, 0.5 to 15 parts by weight of a copolymerizable monomer containing a hydroxyl group, and 0.1 to 5 parts by weight of a crosslinking agent, based on 100 parts by weight of the acrylic polymer,
the antistatic agent is an ionic compound having a melting point of 30 to 50 ℃.
The alkyl (meth) acrylate as the main component is preferably at least one selected from the group consisting of 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, and decyl (meth) acrylate.
The hydroxyl group-containing copolymerizable monomer is preferably 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.
Further, the crosslinking agent is preferably a trifunctional or higher isocyanate compound.
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 formed 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.
The present invention can satisfy all the performances required for the adhesive layer of the surface protective film, which cannot be solved by the prior art.
Detailed Description
The present invention will be described below based on preferred embodiments.
The adhesive composition of the present invention is an adhesive composition containing an antistatic agent, wherein the adhesive composition comprises an acrylic polymer containing an alkyl (meth) acrylate having an alkyl group with 4 to 10 carbon atoms as a main component, and contains 85 to 99.5 parts by weight of the alkyl (meth) acrylate as the main component, 0.5 to 15 parts by weight of a copolymerizable monomer containing a hydroxyl group, and 0.1 to 5 parts by weight of a crosslinking agent, relative to 100 parts by weight of the acrylic polymer, and the antistatic agent is an ionic compound having a melting point of 30 to 50 ℃.
The alkyl (meth) acrylate as the main component is preferably an alkyl (meth) acrylate containing an alkyl group having 4 to 10 carbon atoms, and is preferably at least one compound selected from the group consisting of 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, and decyl (meth) acrylate.
The content of the alkyl (meth) acrylate as the main component is preferably 85 to 99.5 parts by weight with respect to 100 parts by weight of the acrylic polymer.
Examples of the 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 copolymerizable monomer containing a hydroxyl group is preferably 0.5 to 15 parts by weight based on 100 parts by weight of the acrylic polymer.
In the adhesive composition of the present invention, the adhesive composition is preferably crosslinked at the time of forming the adhesive layer. As a method of initiating the crosslinking reaction, crosslinking may be performed by photocrosslinking such as Ultraviolet (UV) light, but it is preferable that the adhesive composition contains a crosslinking agent.
Examples of the crosslinking agent include: a di-or tri-or higher-functional isocyanate compound, a di-or tri-or higher-functional epoxide, a di-or tri-or higher-functional acrylate compound, a metal chelate compound, and the like. Among these, polyisocyanate compounds (di-functional or tri-functional or higher isocyanate compounds) are preferable, and tri-functional or higher isocyanate compounds are more preferable.
The content of the crosslinking agent is preferably 0.1 to 5 parts by weight relative to 100 parts by weight of the acrylic polymer.
The trifunctional or higher isocyanate compound may be a polyisocyanate compound having at least three 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: biuret modified products or isocyanurate modified products of diisocyanates (compounds having two NCO groups in one molecule), and adducts (polyol modified products) of trivalent or higher polyols (compounds having at least three OH groups in one molecule) such as Trimethylolpropane (TMP) or glycerin.
The adhesive composition of the present invention contains an ionic compound having a melting point of 30 to 50 ℃ as an antistatic agent. The antistatic agent may be a quaternary ammonium salt type ionic compound containing an acryloyl group.
These antistatic agents are presumed to have high affinity with acrylic polymers because of their low melting points and long-chain alkyl groups.
The antistatic agent of an ionic compound having a melting point of 30 to 50 ℃ is an ionic compound having a cation and an anion, and includes: 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 -) Boron tetrafluoride (BF)4 -) And the like, inorganic or organic anions. Preferably, the compound is solid at room temperature (e.g., 30 ℃) and can have a melting point of 30 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 antistatic agent as an ionic compound having a melting point of 30 to 50 ℃ is preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the acrylic polymer.
The quaternary ammonium salt type ionic compound having an acryloyl group 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) and the like, and the anion is phosphorus hexafluoride (PF)6 -) Thiocyanate (SCN)-) Organic sulfonic acid Radical (RSO)3 -) Perchlorate (ClO)4 -) Boron tetrafluoride (BF)4 -) F-containing imide group (R)F 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.
Preferably, the acrylic polymer is copolymerized with 0.1 to 5.0% by weight of the quaternary ammonium salt type ionic compound having an acryloyl group.
Specific examples of the antistatic agent are not particularly limited, but specific examples of the ionic compound having a melting point of 30 to 50 ℃ include 1-octylpyridinium dodecylbenzene sulfonate, 1-dodecylpyridinium thiocyanate, 3-methyl-1-dodecylpyridinium hexafluorophosphate, 1-dodecylpyridinium dodecylbenzene sulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate, and the like.
Further, as a specific example of the quaternary ammonium salt type ionic compound having an acryloyl group, dimethylaminomethyl (meth) acrylate methyl hexafluorophosphate [ (CH)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 CH3Dimethylaminomethyl (meth) acrylate 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 crosslinking inhibitor. Examples of the crosslinking inhibitor include: beta-ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, and stearyl acetoacetate, and beta-diketones such as acetylacetone, 2, 4-hexanedione, and benzoylacetone. These are keto-enol tautomeric compounds, and in a binder composition containing a polyisocyanate compound as a crosslinking agent, blocking of an isocyanate group of the crosslinking agent can suppress excessive increase in viscosity or gelation of the binder composition after blending of the crosslinking agent, and can prolong the pot life of the binder composition.
The crosslinking inhibitor is preferably a ketoenol tautomeric compound, and particularly preferably at least one compound selected from the group consisting of acetylacetone and ethyl acetoacetate.
When the crosslinking inhibitor is added, the content of the crosslinking inhibitor is preferably 1.0 to 5.0 parts by weight relative to 100 parts by weight of the acrylic polymer.
The binder composition of the present invention may contain a crosslinking catalyst. In the case where a polyisocyanate compound is used as the crosslinking agent, the crosslinking catalyst may be any one that functions as a catalyst for the reaction (crosslinking reaction) between the acrylic polymer and the crosslinking agent. Examples of the crosslinking catalyst include: and organic metal compounds such as amine compounds such as tertiary amines, organic tin compounds, organic lead compounds, and organic zinc compounds.
Examples of tertiary amines include: trialkylamine, N' -tetraalkyldiamine, N-dialkylaminoalcohol, triethylenediamine, morpholine derivative, piperazine derivative, 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.
The crosslinking catalyst is preferably an organotin compound, and particularly preferably at least one compound selected from the group consisting of dioctyltin oxide and dioctyltin dilaurate.
When the crosslinking catalyst is added, the content of the crosslinking catalyst is preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the acrylic polymer.
The adhesive composition of the present invention may contain a polyether-modified silicone compound. The polyether-modified silicone compound is a silicone compound having a polyether group, except for a general siloxane unit (-SiR)1 2-O-) and siloxane units having polyether groups (-SiR)1(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 12. In addition, when adding, preferably the polyether modified siloxane compound relative to 100 weight portions of the acrylic polymer content is 0.01 ~ 0.5 weight portions. More preferably 0.1 to 0.5 parts by weight.
The HLB is, for example, a hydrophilic-lipophilic balance (a ratio of hydrophilicity to lipophilicity) defined in JIS K3211 (term for surfactant) and the like.
The polyether-modified silicone 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.
The adhesive composition of the present invention may contain a polyether compound. The polyether compound is a compound having a polyalkylene oxide group (polyalkylene oxide), and examples thereof include polyether polyols such as polyalkylene glycols and derivatives thereof. Examples of the alkylene group in the polyalkylene glycol and polyalkylene oxide group include, but are not limited to, ethylene, propylene, and butylene. The polyalkylene glycol may be a copolymer of two or more polyalkylene glycols selected from polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like. 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.
Examples of the polyalkylene glycol derivative include: polyoxyalkylene alkyl ethers such as polyoxyalkylene monoalkyl ethers and polyoxyalkylene dialkyl ethers, polyoxyalkylene alkenyl ethers such as polyoxyalkylene monoalkyl ethers and polyoxyalkylene dialkenyl ethers, polyoxyalkylene aryl ethers such as polyoxyalkylene monoaryl ethers and polyoxyalkylene diaryl ethers, polyoxyalkylene glycol fatty acid esters such as polyoxyalkylene alkylphenyl ethers, polyoxyalkylene glycol monofatty acid esters and polyoxyalkylene glycol difatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene alkylamines, polyoxyalkylene diamines, and the like.
Here, as the alkyl ether in the polyalkylene glycol derivative, there may be mentioned: lower alkyl ethers such as methyl ether and ethyl ether, and higher alkyl ethers such as dodecyl ether and octadecyl ether. Examples of the alkenyl ether in the polyalkylene glycol derivative include vinyl ether, allyl ether, and oleyl ether. In addition, as the fatty acid ester in the polyalkylene glycol derivative, there may be mentioned: saturated fatty acid esters such as acetate and stearate, and unsaturated fatty acid esters such as (meth) acrylate and oleate.
The polyether compound is preferably a compound containing an oxyethylene group (ethylene oxide), and more preferably a compound containing a polyoxyethylene group.
When the polyether compound has a polymerizable functional group, it may be copolymerized with a (meth) acrylic polymer. The polymerizable functional group is preferably an ethylenic functional group such as a (meth) acryl group, a vinyl group, or an allyl group. Examples of the polyether compound having a polymerizable functional group include: polyalkylene glycol mono (meth) acrylates, polyalkylene glycol di (meth) acrylates, alkoxy polyalkylene glycol (meth) acrylates, polyalkylene glycol monoallyl ethers, polyalkylene glycol diallyl ethers, alkoxy polyalkylene glycol allyl ethers, polyalkylene glycol monovinyl ethers, polyalkylene glycol divinyl ethers, alkoxy polyalkylene glycol vinyl ethers, and the like.
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 accelerator, 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 acrylic polymer used as a main agent of the adhesive composition of the present invention can be synthesized by copolymerizing an alkyl (meth) acrylate having an alkyl group with 4 to 10 carbon atoms and a copolymerizable monomer having a hydroxyl group. The method for polymerizing the acrylic polymer is not particularly limited, and an appropriate polymerization method such as solution polymerization or emulsion polymerization can be used.
In the acrylic polymer, other monomers such as a polyalkylene glycol mono (meth) acrylate monomer, a nitrogen-containing vinyl monomer containing no hydroxyl group, an alkoxy group-containing alkyl (meth) acrylate monomer, and an acryl group-containing quaternary ammonium salt type ionic compound may be copolymerized. The acrylic polymer may not contain an acidic copolymerizable monomer such as a carboxyl group-containing copolymerizable monomer.
The adhesive composition of the present invention can be prepared by blending the acrylic polymer with a crosslinking agent, an antistatic agent, and any appropriate additive.
Preferably, the adhesive layer obtained by crosslinking the adhesive composition has an adhesive strength of 0.05 to 0.1N/25mm at a peeling speed of 0.3m/min in a low-speed region and an adhesive strength of 1.0N/25mm or less at a peeling speed of 30m/min in a high-speed region. 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 pressure-sensitive adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition is preferably 5.0X 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". When the surface resistivity of the adhesive layer is large, the adhesive layer has poor performance of releasing static electricity generated by charging when the surface protective film is peeled off. By making the surface resistivity of the adhesive layer sufficiently small, the peeling static voltage generated along with static electricity generated when peeling the adhesive layer from the adherend can be reduced, and the influence on the electric control circuit of the adherend and the like can be suppressed.
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 high at the peeling speed in the low speed region, and the elution of unpolymerized monomers or oligomers from the acrylic polymer 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 performance and excellent balance of adhesive force at peeling speeds in a low speed region and a high speed region because each component of the acrylic polymer is blended in a well-balanced manner. Further, the coating composition is excellent in durability and reworkability (no contamination transferred to an adherend after drawing on a surface protective film with a ballpoint pen via an adhesive layer). Therefore, it can be preferably used for the surface protective film of a polarizing plate.
As the base film of the adhesive layer and the release film (separator) for protecting the adhesive surface, a resin film such as a polyester film can be used.
The base film may be subjected to an anti-fouling treatment with a silicone 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 to be bonded to the adhesive surface of the adhesive layer.
Examples
The present invention will be specifically described below based on examples.
< production of acrylic Polymer >
[ 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, 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of 8-hydroxyoctyl acrylate, and 60 parts by weight of a solvent (ethyl acetate) were added to the reaction apparatus at the same time. 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 acrylic polymer solution 1 having a weight average molecular weight of 50 ten thousand used in example 1.
Examples 2 to 6 and comparative examples 1 to 3
Acrylic polymer solutions used in examples 2 to 6 and comparative examples 1 to 3 were obtained in the same manner as the acrylic polymer solution 1 used in example 1, except that the monomer compositions were adjusted as described in (a) to (B) of table 1.
In tables 1 and 2, (a) is a main component alkyl (meth) acrylate, and (B) is a hydroxyl group-containing copolymerizable monomer.
< production of adhesive composition and surface protective film >
[ example 1]
1.5 parts by weight of 1-octylpyridinium dodecylbenzenesulfonate was added to and stirred with the acrylic polymer solution 1 of example 1 prepared as described above, and then 1.5 parts by weight of CoronateHX (コロネート HX, isocyanurate of hexamethylene diisocyanate compound) was added thereto and stirred and mixed to obtain a binder 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 (D) of table 1.
In tables 1 and 2, (C) is a crosslinking agent, and (D) is an antistatic agent.
TABLE 1
In Table 1, the parenthesized values each represent the weight parts of each component, which are determined based on 100 parts by weight of the total of the groups (A) to (B). In addition, compound names corresponding to abbreviations of the respective components used in table 1 are shown in table 2. Further, Coronate (コロネート, registered trademark) HX, Coronate HL and Coronate L are trade names of Nippon Polyurethane Industrial Co., Ltd., Takenate (タケネート, registered trademark) D-140N, D-127N, D-110N is a trade name of Mitsui chemical Co., Ltd.).
TABLE 2
< 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, then autoclaved at 50 ℃ under 5 atmospheres for 20 minutes, and further left to stand at room temperature for 12 hours, and the surface protective film thus obtained was used as a sample for measuring the adhesion, peeling static voltage, reworkability, and durability.
< adhesion >
The obtained measurement sample (a sample obtained by bonding a 25 mm-wide surface protective film to the surface of a polarizing plate) was peeled in a 180 ° direction at a peeling speed in a low-speed region (0.3m/min) and a peeling speed in a high-speed region (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 using a resistivity meter (trade name: Hiresta (ハイレスタ) UP-HT450, Mitsubishi Chemical analysis co.
< 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 a high-precision electrostatic sensor (model numbers SK-035 and SK-200, manufactured by Keyence Corporation), and the maximum value of the measured values was defined as the peeling electrostatic voltage.
< reworkability >
After the surface protective film of the measurement sample obtained above was drawn with a ball-point pen (load 500g, 3 times back and forth), the surface protective film was peeled off from the polarizing plate, and the surface of the polarizing plate was observed to confirm that no contamination was transferred to the polarizing plate. Evaluation criteria for reworkability: 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. The reworkability was evaluated according to the above criteria.
< 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, and it was confirmed that there was no significant increase in the initial adhesion. Evaluation criteria for durability: 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 durability was evaluated according to the above criteria.
The evaluation results are shown in table 3. 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 3
In the surface protective films of examples 1 to 6, the adhesive strength at a peeling speed of 0.3m/min in a low-speed region was 0.05 to 0.1N/25mm, and the adhesive strength at a peeling speed of 30m/min in a high-speed region was 1.0N/25mm or less; surface resistivity of 5.0 × 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, and the durability after the ballpoint pen was left to stand for 250 hours in an environment of 60 ℃ and 90% RH was also excellent.
That is, all of the following performance requirements are met simultaneously: (1) obtaining the balance of the bonding force under the peeling speed of the low-speed area and the high-speed area; (2) preventing the occurrence of adhesive residue; (3) the antistatic performance is excellent; and (4) has reworkability.
The surface protective film of comparative example 1 was poor in durability, because the amount of alkyl (meth) acrylate as a main component was too small and the amount of the hydroxyl group-containing copolymerizable monomer was too large, and it was low in adhesion at a peeling rate of 0.3m/min in the low speed region, and high in surface resistivity and peeling static voltage.
The surface protective film of comparative example 2 was poor in durability, because the amount of alkyl (meth) acrylate as a main component was too small, the amount of the copolymerizable monomer containing a hydroxyl group was too large, and the antistatic agent was not contained, and it was possible that the adhesive force was small at a peeling speed of 0.3m/min in the low speed region, and the surface resistivity and the peeling static voltage were high.
The surface protective film of comparative example 3 had too high adhesion at a peeling speed of 0.3m/min in a low speed region and high adhesion at a peeling speed of 30m/min in a high speed region, high surface resistivity and peeling static voltage, and poor reworkability and durability, probably because it did not contain a crosslinking agent and an antistatic agent.
As described above, the surface protective films of comparative examples 1 to 3 cannot satisfy all of the following performance requirements at the same time: (1) obtaining the balance of the bonding force under the peeling speed of the low-speed area and the high-speed area; (2) preventing the occurrence of adhesive residue; (3) the antistatic performance is excellent; and (4) has reworkability.
Claims (3)
1. A surface protective film characterized by comprising a resin film and, formed on one or both sides thereof, an adhesive layer obtained by crosslinking an adhesive composition comprising an acrylic polymer, a crosslinking agent and an antistatic agent,
the acrylic polymer comprises an alkyl (meth) acrylate having an alkyl group with 4 to 10 carbon atoms as a main component, and is composed of a copolymer obtained by copolymerizing 85 to 99.5 parts by weight of an alkyl (meth) acrylate as the main component and 5 to 15 parts by weight of a hydroxyl group-containing copolymerizable monomer based on 100 parts by weight of the acrylic polymer,
the adhesive composition contains 0.1 to 5 parts by weight of the crosslinking agent and 0.1 to 5.0 parts by weight of the antistatic agent with respect to 100 parts by weight of the acrylic polymer,
the crosslinking agent is a trifunctional or higher isocyanate compound,
the antistatic agent is an ionic compound having a melting point of 30-50 ℃ and being solid at 30 ℃, and is one or more selected from the group consisting of 1-octylpyridinium dodecylbenzene sulfonate, 1-dodecylpyridinium thiocyanate, 3-methyl-1-dodecylpyridinium hexafluorophosphate, 1-dodecylpyridinium dodecylbenzene sulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate and methyl dimethylaminomethyl (meth) acrylate hexafluorophosphate,
the acrylic polymer does not contain an acidic copolymerizable monomer,
the adhesive layer has an adhesive strength of 0.05 to 0.1N/25mm at a peeling speed of 0.3m/min in a low-speed region and an adhesive strength of 1.0N/25mm or less at a peeling speed of 30m/min in a high-speed region,
the gel fraction of the binder layer is 95-100%.
2. The surface protective film according to claim 1, wherein the main component alkyl (meth) acrylate is one or more selected from the group consisting of 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, and decyl (meth) acrylate.
3. The surface protective film according to claim 1 or 2, wherein 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.
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| JP2012251820A JP6221091B2 (en) | 2012-11-16 | 2012-11-16 | Surface protection film |
| JP2012-251820 | 2012-11-16 | ||
| CN201310556382.1A CN103820059A (en) | 2012-11-16 | 2013-11-11 | Adhesive composition, adhesive film, and surface-protective film |
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| JP6132219B2 (en) | 2013-06-19 | 2017-05-24 | エルジー・ケム・リミテッド | Adhesive composition |
| TWI586781B (en) * | 2013-06-19 | 2017-06-11 | Ｌｇ化學股份有限公司 | Pressure-sensitive adhesive composition |
| JP6198275B2 (en) * | 2014-08-29 | 2017-09-20 | 藤森工業株式会社 | Antistatic surface protection film |
| WO2016068112A1 (en) * | 2014-10-30 | 2016-05-06 | 旭硝子株式会社 | Substrate having antifouling film |
| KR102422205B1 (en) * | 2016-02-25 | 2022-07-18 | 가부시키가이샤 데라오카 세이사쿠쇼 | Adhesive composition and adhesive tape |
| JP6952497B2 (en) * | 2017-05-31 | 2021-10-20 | 日東電工株式会社 | Adhesive composition, surface protective sheet, and optical member |
| JP6529203B2 (en) * | 2018-05-10 | 2019-06-12 | 藤森工業株式会社 | Release film for antistatic surface protection film |
| WO2021199359A1 (en) * | 2020-03-31 | 2021-10-07 | 株式会社寺岡製作所 | Crosslinking-type adhesive agent composition and adhesive tape |
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| KR20140063417A (en) | 2014-05-27 |
| JP2014098128A (en) | 2014-05-29 |
| TWI640592B (en) | 2018-11-11 |
| KR101511088B1 (en) | 2015-04-10 |
| TWI491719B (en) | 2015-07-11 |
| CN103820059A (en) | 2014-05-28 |
| TW201432036A (en) | 2014-08-16 |
| JP6221091B2 (en) | 2017-11-01 |
| TW201708476A (en) | 2017-03-01 |
| CN108300365A (en) | 2018-07-20 |
| TWI630268B (en) | 2018-07-21 |
| TW201534708A (en) | 2015-09-16 |
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