Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • 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
• • 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
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F226/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen

Definitions

• the present invention improves the compatibility between the antistatic agent and the acrylic copolymer containing no acid, thereby suppressing the bleed out of the antistatic agent, thereby improving the durability, antistatic property and corrosion resistance at the same time. It is about.
• a liquid crystal display device In general, a liquid crystal display device (LCD) is provided with a liquid crystal cell and a polarizing plate containing a liquid crystal, and an appropriate pressure-sensitive adhesive layer for bonding them is used.
• the pressure sensitive adhesive is often used an acrylic pressure sensitive adhesive based on an acrylic copolymer having excellent adhesiveness and transparency.
• peeling the release film from the pressure-sensitive adhesive layer generates static electricity.
• the generated static electricity affects the alignment of the liquid crystal and causes defects or flows between the liquid crystal cell and the adhesive due to electrostatic attraction. It causes contamination by foreign objects.
• an ionic antistatic agent is mixed and used in the pressure-sensitive adhesive composition, but a bleed out phenomenon that precipitates due to the surface migration of the ionic antistatic agent may cause lifting, bubbles, and peeling. In particular, this problem may be exacerbated when exposed to a high temperature or high temperature and high humidity environment.
• liquid crystal cell including a metal layer such as ITO is corroded by H 2 O and O 2 contained in the pressure-sensitive adhesive to form metal oxides, hydroxides, and other corrosive products. These may reduce the electrical or mechanical stability of the liquid crystal display, or may cause problems in securing visibility and reliability.
• the present invention is excellent in durability as well as antistatic properties because there is no phenomenon such as lifting, bubbles and peeling due to the surface migration of the antistatic agent, and does not contain a corrosion inhibitor component and can effectively suppress the corrosion of the metal layer.
• the purpose is to provide.
• the present invention provides an adhesive composition containing an acrylic copolymer containing an ionic monomer having a vinyl group, and an ionic antistatic agent.
• the acrylic copolymer may contain a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and an ionic monomer having a vinyl group.
• the ionic monomer having a vinyl group may contain 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
• the ionic antistatic agent is a cation selected from the group consisting of alkali metal salts, ammonium salts, sulfonium salts and phosphonium salts; It may be an ionic salt consisting of an anion selected from the group consisting of fluorine-containing inorganic salts, fluorine-containing organic salts and iodine ions.
• the ionic antistatic agent may contain 0.1 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer.
• the pressure-sensitive adhesive composition may further contain a crosslinking agent.
• the pressure-sensitive adhesive composition of the present invention does not have a phenomenon such as lifting, bubbles, and peeling due to the surface migration of the antistatic agent, which is excellent in durability and at the same time has an advantage of satisfying the antistatic property.
• the pressure-sensitive adhesive composition of the present invention has an advantage of effectively suppressing corrosion of the metal layer without separately containing a corrosion inhibitor component.
• the pressure-sensitive adhesive composition is expected to have high utility for anti-static applications in the fields of plastic products, especially electrical / electronic devices, which tend to generate static electricity.
• the present invention improves the compatibility between the antistatic agent and the acrylic copolymer containing no acid, thereby suppressing the bleed out of the antistatic agent, thereby improving the durability, antistatic property and corrosion resistance at the same time. It is about.
• the adhesive composition of this invention contains the acrylic copolymer containing the ionic monomer which has a vinyl group, and an ionic antistatic agent.
• the pressure-sensitive adhesive composition of the present invention improves the compatibility of the ionic antistatic agent by the ionic monomer immobilized by the polymerization reaction of the acrylic copolymer,
• the bleed out phenomenon in which the antistatic agent component moves to the surface and precipitates is suppressed by the improvement of the compatibility, and the durability is excellent. This phenomenon can be suppressed even under high temperature or high temperature / humidity environment, thereby maintaining excellent durability.
• the ionic monomer since the ionic monomer has an antistatic property together with the ionic antistatic agent, its performance is significantly improved as compared with the pressure-sensitive adhesive composition using a conventional antistatic agent alone.
• the ionic monomer contained in the acrylic copolymer includes a vinyl group so as to be copolymerizable with the acrylate monomer, and may be used to form an ionic bond with the ionic antistatic agent.
• the ionic monomer or Can be Specifically, the ionic monomer or Can be.
• ionic monomers can be prepared by commercially available products or by synthesis, for example the synthesis can be used the method of US Pat. No. 3,226,881.
• the acryl-type copolymer of this invention contains the (meth) acrylate monomer which has a C1-C12 alkyl group, and the ionic monomer which has a vinyl group.
• (meth) acrylate means acrylate and methacrylate.
• Examples of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth).
• the said ionic monomer which has a vinyl group contains 0.1-10 weight part with respect to 100 weight part of (meth) acrylate monomers which have a C1-C12 alkyl group, More preferably, it is 0.5-5 weight part. If the content is less than 0.1 parts by weight, it may be difficult to secure durability due to insufficient compatibility improvement effect of the antistatic agent, and if it exceeds 10 parts by weight, it may be difficult to secure moisture and heat resistance due to excessively high hydrophilicity.
• the acrylic copolymer of the present invention may further contain a polymerizable monomer having a crosslinkable functional group in addition to the ionic monomer having a vinyl group.
• the polymerizable monomer having a crosslinkable functional group uses a component that does not generate hydrogen ions (H + ), which can impart cohesion or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding to impart durability and cutting properties.
• Examples of the polymerizable monomer having a crosslinkable functional group include a monomer having a hydroxy group, a monomer having an amide group, a monomer having a tertiary amine group, and the like, and these may be used alone or in combination of two or more thereof.
• Examples of the monomer having an amide group include (meth) acrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, 6 -Hydroxyhexyl (meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide, 2-hydroxyethylhexyl (meth) acrylamide, etc. are mentioned, Among these, (meth) acrylamide is preferable.
• Monomers having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) acrylate, and N, N- (dimethylamino) propyl ( Meth) acrylate, etc. are mentioned.
• the polymerizable monomer which has such a crosslinkable functional group is contained in 0.05-10 weight part with respect to 100 weight part of (meth) acrylate monomers which have a C1-C12 alkyl group, More preferably, it is 0.1-8 weight part good. If the content is less than 0.05 parts by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, the durability may be lowered. If the content is more than 10 parts by weight, the adhesive strength is lowered by a high gel fraction may cause problems in durability.
• the acrylic copolymer of the present invention may further contain other polymerizable monomers other than the above monomers in a range of not lowering the adhesive strength, for example, 10 parts by weight or less based on the total amount.
• the production method of the copolymer is not particularly limited, and may be prepared using a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable.
• a solvent, a polymerization initiator, a chain transfer agent for molecular weight control, and the like, which are usually used in the polymerization may be used.
• the acrylic copolymer preferably has a weight average molecular weight (polystyrene equivalent, Mw) measured by gel permeation chromatography (GPC) of 50,000 to 2 million, more preferably 400,000 to 2 million. If the weight average molecular weight is less than 50,000, there is a lack of cohesion between the copolymers may cause problems in adhesion durability, if the weight average molecular weight is more than 2 million may require a large amount of dilution solvent to ensure fairness during coating.
• Mw polystyrene equivalent
• the ionic antistatic agent is not particularly limited as long as it is an ionic salt composed of an anion and a cation and can impart ionic conductivity to the pressure-sensitive adhesive.
• a cation selected from the group consisting of alkali metal salts, ammonium salts, sulfonium salts and phosphonium salts; It may be an ionic salt consisting of an anion selected from the group consisting of fluorine-containing inorganic salts, fluorine-containing organic salts and iodine ions.
• Such an ionic antistatic agent may contain 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.1 parts by weight may be insufficient antistatic properties and if it exceeds 10 parts by weight it may be difficult to secure durability.
• the pressure-sensitive adhesive composition of the present invention may further contain a crosslinking agent.
• a crosslinking agent can improve adhesiveness and durability, and can maintain the reliability and shape of an adhesive at high temperature.
• the crosslinking agent may be an isocyanate type, an epoxy type, a melamine type, a peroxide type, a metal chelate type, an oxazoline type, or the like, and one or two or more kinds thereof may be used. Double isocyanate type or epoxy type is preferred.
• the isocyanate type is tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, naphthalenedi Diisocyanate compounds such as isocyanate; Diisocyanate obtained from 2 moles of an adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate obtained by self-condensing 3 moles of the diisocyanate compound, and 3 moles of the diisocyanate compound And polyfunctional isocyanate compounds containing three functional groups such as biuret, triphenylmethanetriisocyanate, and methylenebistriisocyanate, in which the remaining 1 mo
• Examples of the melamine type include hexametholol melamine, hexamethoxymethyl melamine, hexabutoxymethyl melamine, and the like.
• Such a crosslinking agent may be contained in an amount of 0.1 to 15 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.1 part by weight, the cohesive force may be reduced due to insufficient crosslinking degree, thereby impairing the adhesive durability and the cleavage property. If the content is more than 15 parts by weight, problems may occur in reducing residual stress due to excessive crosslinking reaction.
• the pressure-sensitive adhesive composition is a silane coupling agent, tackifying resin, antioxidant, leveling agent, surface lubricant, dye, in order to adjust the adhesion, cohesion, viscosity, elastic modulus, glass transition temperature, etc.
• Additives, such as a pigment, an antifoamer, a filler, and a light stabilizer, can be further contained.
• Such additives can be appropriately adjusted in a range not impairing the effects of the present invention.
• the pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive for polarizing plates and a surface protective film for bonding to liquid crystal cells.
• it can be used as a general commercial adhesive sheet product as well as a protective film, a reflective sheet, a structural adhesive sheet, a photographic adhesive sheet, a lane marking adhesive sheet, an optical adhesive product, an adhesive for electronic parts, and the like.
• n-butyl acrylate BA
• MA methyl acrylate
• 2-hydroxyethyl acrylate 2.0 85 parts by weight of n-butyl acrylate (BA), 8 parts by weight of methyl acrylate (MA), 2-hydroxyethyl acrylate 2.0 in a 1 L reactor equipped with a refrigeration system to facilitate nitrogen temperature reflux and temperature control.
• Weight After adding a monomer mixture consisting of 5 parts by weight of an ionic monomer of 100 parts by weight of acetone as a solvent. Then, after purging nitrogen gas for 1 hour to remove oxygen, it was maintained at 62 °C. After homogenizing the mixture, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 6 hours to prepare an acrylic copolymer having a weight average molecular weight of about 1 million.
• AIBN azobisisobutyronitrile
• an acrylic copolymer, an ionic antistatic agent, a crosslinking agent (Japan urethane CORONATE-L, 0.5 parts) and a silane coupling agent (Shin-Etsu Co., Ltd. KBM-403, 0.5 parts) were mixed, and then diluted with ethyl acetate to solid content.
• a pressure-sensitive adhesive composition having a concentration of 15% was prepared.
• Table 1 describes the acrylic copolymer and the ionic antistatic agent, and other crosslinking agents and silane coupling agents used the same components and contents.
• the pressure-sensitive adhesive composition prepared above was applied on a release film coated with a silicone release agent to have a thickness of 25 ⁇ m, and dried at 100 ° C. for 1 minute to form an adhesive layer.
• a pressure-sensitive adhesive polarizing plate was prepared by laminating the pressure-sensitive adhesive layer prepared above on an iodine-based polarizing plate having a thickness of 185 ⁇ m. The prepared polarizing plate was stored for 20 days under conditions of 23 degreeC and 60% RH.
• the prepared pressure-sensitive adhesive polarizing plate was measured 10 times each of three points of the pressure-sensitive adhesive layer using a surface resistance measuring instrument (MCP-HT450, Mitsubishi Chemical Co., Ltd.), and the average value thereof was represented.
• Bubble or peeling is slightly visible but polarizer performance is maintained: ⁇
• the adhesive layer was peeled from the said laminated body, the surface of the aluminum plate which contacted the said adhesive layer was visually observed, and the presence or absence of corrosion was evaluated.
• the aluminum plate surface is not corroded at all: ⁇
• the pressure-sensitive adhesive composition of Examples 1 to 8 containing the acrylic copolymer containing the ionic monomer having a vinyl group and the ionic antistatic agent according to the present invention has a durability (heat resistance and Heat resistance), antistatic properties and corrosion resistance was confirmed to be excellent at the same time.

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• Chemical Kinetics & Catalysis (AREA)
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• 2012
  • 2012-09-04 KR KR1020120097729A patent/KR101887570B1/ko active IP Right Grant
• 2013
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