WO2011115224A1 - Pressure-sensitive adhesive composition for optical members and pressure-sensitive adhesive tape for optical members - Google Patents

Pressure-sensitive adhesive composition for optical members and pressure-sensitive adhesive tape for optical members Download PDF

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Publication number
WO2011115224A1
WO2011115224A1 PCT/JP2011/056467 JP2011056467W WO2011115224A1 WO 2011115224 A1 WO2011115224 A1 WO 2011115224A1 JP 2011056467 W JP2011056467 W JP 2011056467W WO 2011115224 A1 WO2011115224 A1 WO 2011115224A1
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WO
WIPO (PCT)
Prior art keywords
sensitive adhesive
pressure
weight
monomer
adhesive composition
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Application number
PCT/JP2011/056467
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French (fr)
Japanese (ja)
Inventor
耕平 丸尾
智基 戸田
康晴 永井
拓道 杉原
Original Assignee
積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN201180013744.1A priority Critical patent/CN102791817B/en
Priority to KR1020127026981A priority patent/KR101938894B1/en
Priority to JP2011513787A priority patent/JP5727371B2/en
Publication of WO2011115224A1 publication Critical patent/WO2011115224A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08Homopolymers or copolymers of acrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J139/00Adhesives 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
    • C09J139/04Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C09J139/06Homopolymers or copolymers of N-vinyl-pyrrolidones
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/10Adhesives in the form of films or foils without carriers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385Acrylic polymers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition for an optical member that can suppress whitening that occurs under high temperature and high humidity and realize high reliability. Moreover, this invention relates to the adhesive tape for optical members manufactured using this adhesive composition for optical members.
  • Display panels are used in various fields, and particularly in mobile phones, personal digital assistants, etc., they are used not only for image display devices but also for input devices.
  • the display panel is bonded to a protective plate, a touch panel, an optical filter, or the like that protects the surface with a highly transparent adhesive such as an acrylic adhesive or an adhesive tape. .
  • Patent Document 1 discloses an acrylic transparent pressure-sensitive adhesive composition obtained by polymer blending an ABA triblock copolymer composed of an acrylic ester and a methacrylic ester and a resin having a hydroxyl group. It is disclosed.
  • the acrylic transparent pressure-sensitive adhesive composition described in the same document has transparency without whitening even when exposed to an environment such as a high-temperature and high-humidity environment, a hot-water immersion environment, or a boiling environment for a long time. It is stated that it can be maintained.
  • the acrylic transparent pressure-sensitive adhesive composition described in Patent Document 1 has a low molecular weight resin having a hydroxyl group to be blended, and therefore has such properties as pressure-sensitive adhesive properties and heat resistance that are originally required for a pressure-sensitive adhesive or pressure-sensitive adhesive tape. It ’s not enough. Accordingly, there is a need for a new pressure-sensitive adhesive or pressure-sensitive adhesive tape that can simultaneously suppress whitening that occurs under high temperature and high humidity without reducing the reliability of the pressure-sensitive adhesive or pressure-sensitive adhesive tape.
  • An object of this invention is to provide the adhesive composition for optical members which can suppress the whitening which arises under high temperature, high humidity, and can implement
  • the present invention is an adhesive composition for an optical member containing an acrylic copolymer, the acrylic copolymer comprising 1 to 25% by weight of 2-hydroxyethyl acrylate, 1 to 25% by weight of N-vinylpyrrolidone, 0.5 to 30% by weight of a monomer having a structure represented by the following general formula (1-1), or 0.1 to 30% by weight of a monomer having a structure represented by the following general formula (1-2) It is the adhesive composition for optical members obtained by superposing
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom or an alkyl group having less than 3 carbon atoms
  • n represents an integer of 8 to 45.
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group having 3 to 30 carbon atoms
  • m represents an integer of 8 to 45.
  • the present inventors use a highly hydrophilic monomer as a monomer constituting the acrylic copolymer, so that it is exposed to room temperature after being exposed to high temperature and high humidity. It was found that water was finely dispersed when it was returned to, and as a result, whitening could be suppressed.
  • the present inventors have found that many of the highly hydrophilic monomers increase the glass transition temperature (Tg) of the acrylic copolymer more than necessary and are not suitable for the pressure-sensitive adhesive composition, whereas 2-hydroxyethyl acrylate, By using N-vinylpyrrolidone or a specific monomer having a polyethylene oxide chain at a predetermined ratio, whitening that occurs under high temperature and high humidity can be suppressed, and high reliability can be realized. It discovered that the adhesive composition for members was obtained, and came to complete this invention.
  • the pressure-sensitive adhesive composition for optical members of the present invention contains an acrylic copolymer.
  • the acrylic copolymer is composed of 1 to 25% by weight of 2-hydroxyethyl acrylate, 1 to 25% by weight of N-vinylpyrrolidone, and 0.5 to 30% by weight of a monomer having a structure represented by the following general formula (1-1) %, Or a mixed monomer containing 0.1 to 30% by weight of a monomer having a structure represented by the following general formula (1-2).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom or an alkyl group having less than 3 carbon atoms
  • n represents an integer of 8 to 45.
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group having 3 to 30 carbon atoms
  • m represents an integer of 8 to 45.
  • 2-hydroxyethyl acrylate, N-vinylpyrrolidone, a monomer having a structure represented by the general formula (1-1), and a monomer having a structure represented by the general formula (1-2) are hydrophilic groups. And has high hydrophilicity. Therefore, when the above-mentioned mixed monomer contains these monomers in a proportion within the above range, the pressure-sensitive adhesive composition for an optical member of the present invention can absorb water when it is returned to room temperature after being exposed to high temperature and high humidity. Fine dispersion is achieved, and as a result, whitening can be suppressed.
  • the monomer is also referred to as “monomer having a hydrophilic group”. Further, the monomer having a hydrophilic group does not unnecessarily increase the glass transition temperature (Tg) of the acrylic copolymer, and adversely affects the reliability of the pressure-sensitive adhesive composition for optical members of the present invention. There is nothing.
  • the adhesive composition for optical members of the present invention contains a monomer having a whitening that occurs under high temperature and high humidity even when a metal thin film containing a metal or metal oxide such as ITO is used as an adherend. Can be suppressed.
  • a highly hydrophilic monomer that has an effect of suppressing whitening and does not adversely affect reliability
  • a highly hydrophilic monomer that has an effect of suppressing whitening and does not adversely affect reliability
  • 4-hydroxybutyl acrylate (4- HBA) 3-hydroxypropyl acrylate (3-HPA)
  • 6-hydroxyhexyl acrylate (6-HHA) and the like for example, 4-hydroxybutyl acrylate (4- HBA), 3-hydroxypropyl acrylate (3-HPA), 6-hydroxyhexyl acrylate (6-HHA) and the like.
  • the mixed monomer may contain these highly hydrophilic monomers.
  • a pressure-sensitive adhesive composition for an optical member having high initial adhesiveness and capable of maintaining high adhesiveness even after time has been obtained, and further, a metal such as ITO or a metal A monomer having a structure represented by the above general formula (1-1) can be more effectively suppressed whitening that occurs under high temperature and high humidity when a metal thin film containing an oxide is used as an adherend.
  • a monomer having a structure represented by the general formula (1-2) is preferable.
  • the monomer having the hydrophilic group is 2-hydroxyethyl acrylate or N-vinylpyrrolidone.
  • the monomer having a hydrophilic group is a monomer having a structure represented by the general formula (1-1) or a monomer having a structure represented by the general formula (1-2). Therefore, it is possible to prevent the gelation of the pressure-sensitive adhesive composition for optical members from proceeding rapidly depending on the type or amount of the crosslinking agent, and the type and amount of the crosslinking agent can be easily controlled.
  • the number of ethylene oxide repeats is 8 for the lower limit and 8 for the upper limit. 45.
  • the number of ethylene oxide repeats is less than 8
  • the resulting pressure-sensitive adhesive composition for optical members cannot sufficiently suppress whitening that occurs under high temperature and high humidity.
  • the number of ethylene oxide repeats exceeds 45, the resulting pressure-sensitive adhesive composition for optical members cannot sufficiently suppress whitening that occurs under high temperature and high humidity.
  • the ethylene oxide repeat number exceeds 45, a monomer having a structure represented by the general formula (1-1) or a monomer having a structure represented by the general formula (1-2) Compatibility with other main components such as monomers decreases, and the resulting pressure-sensitive adhesive composition for optical members has reduced adhesive strength. Since the repetition number of the ethylene oxide can more effectively suppress whitening that occurs under high temperature and high humidity, the preferable lower limit is 13 and the preferable upper limit is 40. The number of ethylene oxide repeats is particularly preferably 30. The repeating number of ethylene oxide is represented by n in the general formula (1-1) and represented by m in the general formula (1-2).
  • the terminal group of the polyethylene oxide chain is a hydrogen atom or an alkyl group having less than 3 carbon atoms. Especially, since the adhesive composition for optical members which can suppress whitening also on conditions of higher temperature and humidity is obtained, an alkyl group with less than 3 carbon atoms is preferable.
  • the terminal group of the polyethylene oxide chain is represented by R 2 in the general formula (1-1).
  • the end group of the polyethylene oxide chain is an alkyl group having 3 to 30 carbon atoms.
  • the terminal group of the polyethylene oxide chain is preferably an alkyl group having 18 carbon atoms because a pressure-sensitive adhesive composition for an optical member that can suppress whitening even under conditions of higher temperature and higher humidity is obtained.
  • the end group of the polyethylene oxide chain is represented by R 4 in the general formula (1-2).
  • the obtained pressure-sensitive adhesive composition for optical members cannot sufficiently suppress whitening that occurs under high temperature and high humidity.
  • the ratio of the monomer having the hydrophilic group in the mixed monomer is too large, the pressure-sensitive adhesive layer made of the obtained pressure-sensitive adhesive composition for optical members has reduced initial wettability, and adhesion to an adherend. Lower and less reliable.
  • the proportion of 2-hydroxyethyl acrylate or N-vinylpyrrolidone in the mixed monomer is preferably 5% by weight, more preferably 8% by weight, more preferably 20% by weight, and still more preferably 15% by weight. is there.
  • the proportion of the monomer having the structure represented by the general formula (1-1) in the mixed monomer or the monomer having the structure represented by the general formula (1-2) is preferably 1% by weight as a lower limit.
  • a more preferred lower limit is 2% by weight, a preferred upper limit is 20% by weight, and a more preferred upper limit is 15% by weight.
  • the mixed monomer preferably contains 10 to 60% by weight of a monomer having a bicyclo ring structure and one olefinic double bond.
  • the pressure-sensitive adhesive composition for an optical member obtained has dramatically improved adhesive strength to an adherend. Such an improvement in adhesive strength exhibits a particularly excellent effect when the adherend is a polycarbonate plate or an acrylic plate.
  • the polycarbonate plate and the acrylic plate easily absorb moisture, and the moisture is vaporized under high temperature conditions to generate outgas. Therefore, when the adherend is a polycarbonate plate or an acrylic plate, bubbles grow due to the gas pressure of the outgas under high temperature conditions, and the interface between the polycarbonate plate or the acrylic plate and the pressure-sensitive adhesive layer tends to float off.
  • the mixed monomer contains a monomer having the bicyclo ring structure and one olefinic double bond
  • the resulting pressure-sensitive adhesive composition for an optical member has dramatically improved adhesion to an adherend, Even when the adherend is a polycarbonate plate or an acrylic plate, it is possible to suppress the floating peeling that occurs at the interface between the adherend and the pressure-sensitive adhesive layer.
  • the polycarbonate plate and the acrylic plate are used for, for example, a touch panel of an input device such as a mobile phone or a portable information terminal.
  • the bicyclo ring structure is not particularly limited, and examples of the functional group having the bicyclo ring structure include a bicyclo [1.1.0] butyl group, a bicyclo [1.1.1] pentyl group, and a bicyclo [2.1.
  • the said substitution may be one place and may be multiple places.
  • a functional group which has the said bicyclo ring structure a norbornyl group and an isobornyl group are preferable and an isobornyl group is especially preferable.
  • the olefinic double bond is not particularly limited, and examples of the functional group having the olefinic double bond include a (meth) acryloyl group, a vinyl group, and an allyl group. Of these, a (meth) acryloyl group is preferred as the functional group having the olefinic double bond.
  • the monomer having the bicyclo ring structure and one olefinic double bond for example, isobornyl (meth) acrylate having an isobornyl group and a (meth) acryloyl group is preferable.
  • the resulting pressure-sensitive adhesive composition for optical members has a reduced adhesive force to the adherend.
  • reliability may be reduced.
  • the ratio of the monomer having the bicyclo ring structure and one olefinic double bond in the mixed monomer exceeds 60% by weight, the glass transition temperature of the resulting acrylic copolymer may increase.
  • the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical members containing such an acrylic copolymer the adhesiveness to the adherend is lowered, and the reliability may be lowered.
  • the ratio of the monomer having the bicyclo ring structure and one olefinic double bond in the mixed monomer is more preferably a lower limit of 15% by weight, a still more preferable lower limit of 25% by weight, and a more preferable upper limit of 55% by weight, still more preferable.
  • the upper limit is 40% by weight.
  • the mixed monomer preferably contains 30 to 80% by weight of a (meth) acrylic acid ester monomer having a structure represented by the following general formula (2).
  • the (meth) acrylic acid ester monomer having a structure represented by the following general formula (2) is also simply referred to as “(meth) acrylic acid ester monomer”.
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 represents an alkyl group having 3 to 14 carbon atoms.
  • the hydrogen atom of the alkyl group of R 6 may be substituted with a cycloalkyl group.
  • the glass transition temperature of the resulting acrylic copolymer may be increased.
  • the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for an optical member containing such an acrylic copolymer may deteriorate in reliability due to a decrease in adhesion to an adherend.
  • the alkyl group of R 6 preferably has 4 to 12 carbon atoms.
  • the hydrogen atom of the alkyl group of R 6 may be substituted with a cycloalkyl group.
  • the cycloalkyl group is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • the (meth) acrylic acid ester monomer is not particularly limited.
  • the pressure-sensitive adhesive layer made of the obtained pressure-sensitive adhesive composition for optical members is improved in cohesive force, initial adhesiveness, adhesion and the like.
  • the (meth) acrylic acid ester monomer includes 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate and butyl ( It is preferable to contain at least one (meth) acrylic acid ester monomer selected from the group consisting of (meth) acrylates.
  • the resulting pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical members has a high low-temperature elastic modulus and initial wettability. May decrease, adhesion to an adherend may decrease, and reliability may decrease.
  • the proportion of the (meth) acrylic acid ester monomer in the mixed monomer exceeds 80% by weight, the pressure-sensitive adhesive layer made of the resulting pressure-sensitive adhesive composition for optical members has reduced cohesive force and processability.
  • a more preferable lower limit is 40% by weight, and a more preferable upper limit is 65% by weight.
  • the mixed monomer may contain a monomer having a carboxyl group and one olefinic double bond.
  • the mixed monomer contains a monomer having the carboxyl group and one olefinic double bond
  • the resulting acrylic copolymer has an increased intermolecular interaction.
  • the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical members containing such an acrylic copolymer has improved cohesive strength.
  • the said mixed monomer does not need to contain the monomer which has the said carboxyl group and one olefinic double bond.
  • the monomer which has the said carboxyl group and one olefinic double bond is not specifically limited, For example, (meth) acrylic acid, (meth) acryloyl acetic acid, (meth) acryloyl propionic acid, (meth) acryloyl butyric acid, (meth ) Unsaturated monocarboxylic acids such as acryloylpentanoic acid and crotonic acid, and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid.
  • the ratio of the monomer having the carboxyl group and one olefinic double bond in the mixed monomer is not particularly limited, but is preferably 2% by weight or less. When the ratio of the monomer having the carboxyl group and one olefinic double bond exceeds 2% by weight, the resulting pressure-sensitive adhesive composition for an optical member is obtained from a metal thin film containing a metal such as ITO or a metal oxide. In the case of an adherend, the metal thin film may be easily deteriorated.
  • the ratio of the monomer having the carboxyl group and one olefinic double bond in the mixed monomer is more preferably 1% by weight or less, and further preferably 0.5% by weight or less.
  • the method for producing the acrylic copolymer is not particularly limited.
  • the monomer having the hydrophilic group and the monomer having the bicyclo ring structure and one olefinic double bond to be blended as necessary.
  • a method of radical polymerization of a mixed monomer containing other monomers in the presence of a polymerization initiator is not particularly limited.
  • the said polymerization method is not specifically limited, For example, conventionally well-known polymerization methods, such as solution polymerization, emulsion polymerization, suspension polymerization, block polymerization, are mentioned.
  • the solvent used for the solution polymerization is not particularly limited, and examples thereof include ethyl acetate, toluene, dimethyl sulfoxide, ethanol, acetone, diethyl ether and the like.
  • the compounding quantity of the solvent used for the said solution polymerization is not specifically limited,
  • the preferable minimum with respect to 100 weight part of said mixed monomers is 25 weight part, and a preferable upper limit is 300 weight part.
  • the blending amount of the solvent is less than 25 parts by weight, the molecular weight distribution of the resulting acrylic copolymer may be broadened.
  • the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for an optical member containing such an acrylic copolymer may reduce the adhesive force and cohesive force with respect to the adherend, thereby reducing the reliability.
  • the amount of the solvent exceeds 300 parts by weight, it is necessary to remove the solvent when preparing the pressure-sensitive adhesive composition for an optical member using the resulting acrylic copolymer and forming the pressure-sensitive adhesive layer. May be.
  • the said polymerization initiator is not specifically limited, For example, a persulfate, an organic peroxide, an azo compound etc. are mentioned. Among these, an azo compound is preferable in consideration of the influence on the metal thin film when a metal thin film containing a metal such as ITO or a metal oxide is used as an adherend.
  • the persulfate is not particularly limited, and examples thereof include potassium persulfate, sodium persulfate, and ammonium persulfate.
  • the organic peroxide is not particularly limited.
  • the azo compound is not particularly limited.
  • These polymerization initiators may be used alone or in combination of two or more.
  • the preferable minimum with respect to 100 weight part of said mixed monomers is 0.02 weight part, and a preferable upper limit is 0.5 weight part.
  • a preferable upper limit is 0.5 weight part.
  • the blending amount of the polymerization initiator is less than 0.02 parts by weight, the polymerization reaction may be insufficient, or the polymerization reaction may take a long time.
  • the blending amount of the polymerization initiator exceeds 0.5 parts by weight, the weight average molecular weight of the resulting acrylic copolymer may become too low or the molecular weight distribution may become too wide.
  • the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for an optical member containing such an acrylic copolymer may reduce the adhesive force and cohesive force with respect to the adherend, thereby reducing the reliability.
  • a preferable lower limit is 200,000 and a preferable upper limit is 1,500,000.
  • the pressure-sensitive adhesive layer made of the obtained pressure-sensitive adhesive composition for optical members may have a reduced high-temperature elastic modulus and a reduced reliability.
  • the weight average molecular weight of the acrylic copolymer exceeds 1,500,000, the fluidity of the acrylic copolymer may be lowered.
  • the adhesiveness to the adherend is lowered, and the reliability may be lowered.
  • the more preferable lower limit of the weight average molecular weight of the acrylic copolymer is 300,000, the still more preferable lower limit is 400,000, the still more preferable lower limit is 500,000, the more preferable upper limit is 1,200,000, and the still more preferable upper limit is 900,000.
  • a preferable upper limit is 650,000.
  • a weight average molecular weight means the value measured by gel permeation chromatography (GPC) method and calculated
  • GPC gel permeation chromatography
  • the diluted solution obtained by diluting the acrylic copolymer 100 times with tetrahydrofuran (THF) is filtered through a filter, and the obtained filtrate is filtered with a column (for example, a product name manufactured by Waters).
  • the weight average molecular weight can be determined by polystyrene conversion using a “2690 Separations Model” or the like.
  • the solution containing the acrylic copolymer is a low viscosity solution. Therefore, when forming the pressure-sensitive adhesive layer using the pressure-sensitive adhesive composition for optical members containing the acrylic copolymer, the amount of the solvent required for coating is small, and the handleability is excellent. Moreover, it is easy to produce a thick adhesive layer, and the adhesive force of the adhesive layer to the adherend can be increased.
  • the viscosity of the pressure-sensitive adhesive composition solution for an optical member containing the acrylic copolymer is not particularly limited, but a B-type viscometer (“B8U-type viscometer”, manufactured by Tokyo Keiki Co., Ltd.) is used at a temperature of 25 ° C.
  • the preferable lower limit of the measured viscosity is 500 mPa ⁇ s, and the preferable upper limit is 100,000 mPa ⁇ s.
  • the pressure-sensitive adhesive composition for an optical member of the present invention may contain a crosslinking agent in addition to the acrylic copolymer.
  • a crosslinked structure can be formed in the acrylic copolymer.
  • the gel fraction of the adhesive layer which consists of an adhesive composition for optical members obtained by adjusting the kind or quantity of the said crosslinking agent suitably can be adjusted.
  • the said crosslinking agent is not specifically limited, For example, an isocyanate type crosslinking agent, an aziridine type crosslinking agent, an epoxy-type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned.
  • the adhesive composition for optical members of this invention is at least 1 bridge
  • an aliphatic isocyanate type crosslinking agent is preferable.
  • examples of commercially available products include Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.).
  • examples of commercially available products include Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.).
  • examples of commercially available products include Denacol EX212 and Denacol EX214 (both manufactured by Nagase ChemteX Corporation).
  • the preferable minimum with respect to 100 weight part of said acrylic copolymers is 0.1 weight part, and a preferable upper limit is 10 weight part.
  • the blending amount of the crosslinking agent is less than 0.1 parts by weight, the acrylic copolymer is insufficiently crosslinked, and the pressure-sensitive adhesive layer made of the resulting pressure-sensitive adhesive composition for optical members has reduced cohesive force. As a result, workability may be reduced.
  • the blending amount of the crosslinking agent exceeds 10 parts by weight, the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical members is deteriorated in the adhesive strength and initial adhesiveness to the adherend, and the reliability is lowered.
  • the more preferable minimum with respect to 100 weight part of said acrylic copolymers is 0.3 weight part, and a more preferable upper limit is 3.0 weight part.
  • the pressure-sensitive adhesive composition for optical members of the present invention may further contain a tackifier resin.
  • the tackifying resin is not particularly limited, and examples thereof include a xylene resin, a phenol resin, a rosin resin, and a terpene resin. These tackifier resins may be used alone or in combination of two or more. Of these, a xylene resin is preferable, and an alkylphenol reaction product of the xylene resin is more preferable.
  • a hydrogenated resin is preferable. By using such a hydrogenated resin, the pressure-sensitive adhesive composition for an optical member obtained has increased transparency.
  • the pressure-sensitive adhesive composition for optical members of the present invention may further contain a silane coupling agent.
  • a silane coupling agent By containing the said silane coupling agent, the adhesive layer which consists of an adhesive composition for optical members obtained improves the adhesiveness with respect to a to-be-adhered body.
  • the silane coupling agent is not particularly limited.
  • the pressure-sensitive adhesive composition for an optical member of the present invention may further contain a conventionally known additive as necessary within the range not impairing the effects of the present invention.
  • the said additive is not specifically limited, For example, a filler, anti-aging agent, etc. are mentioned.
  • the method for producing the pressure-sensitive adhesive composition for optical members of the present invention is not particularly limited.
  • the acrylic copolymer, and, if necessary, the crosslinking agent, the tackifying resin, the silane coupling agent, The method of mixing and stirring the said additive is mentioned.
  • the application of the pressure-sensitive adhesive composition for optical members of the present invention is not particularly limited, and can be applied to various optical members.
  • the adhesive tape for optical members which has an adhesive layer which consists of an adhesive composition for optical members of this invention is also one of this invention.
  • the gel fraction of the said adhesive layer is not specifically limited, although it can adjust suitably according to the use of the adhesive tape for optical members, a preferable minimum is 30 weight% and a preferable upper limit is 95 weight%.
  • a preferable minimum is 30 weight% and a preferable upper limit is 95 weight%.
  • the gel fraction of the pressure-sensitive adhesive layer is less than 30% by weight, the processability of the pressure-sensitive adhesive tape for optical members may be lowered.
  • the gel fraction of the pressure-sensitive adhesive layer exceeds 95% by weight, the initial wettability of the pressure-sensitive adhesive layer is lowered, the adhesion to the adherend is lowered, and the reliability may be lowered.
  • the minimum with a more preferable gel fraction of the said adhesive layer is 40 weight%, and a more preferable upper limit is 90 weight%.
  • the gel fraction can be measured by the following method. First, the pressure-sensitive adhesive tape for optical members of the present invention is cut into a flat rectangular shape of 50 mm ⁇ 25 mm to produce a test piece. The pressure-sensitive adhesive layer of the obtained test piece was scraped with a spoon to prepare a pressure-sensitive adhesive lump. After the pressure-sensitive adhesive lump was immersed in ethyl acetate at 23 ° C. for 24 hours, a 200-mesh stainless mesh was The mass of the pressure-sensitive adhesive is taken out from the ethyl acetate and dried at 110 ° C. for 1 hour. And the weight of the lump of the adhesive after drying is measured, and a gel fraction is computed using following formula (1).
  • the thickness of the said adhesive layer is not specifically limited, A preferable minimum is 5 micrometers and a preferable upper limit is 1 mm.
  • a more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 10 ⁇ m, a further preferable lower limit is 20 ⁇ m, a more preferable upper limit is 500 ⁇ m, and a further preferable upper limit is 300 ⁇ m.
  • the pressure-sensitive adhesive tape for optical members of the present invention may be a non-support type that does not have a base material, or may be a support type in which pressure-sensitive adhesive layers are formed on both surfaces of the base material.
  • the base material is not particularly limited as long as it is a transparent base material.
  • the base material is made of a transparent resin such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), nylon, urethane, and polyimide. Examples thereof include a sheet, a sheet having a network structure, and a sheet having holes.
  • the thickness of the said base material is not specifically limited, A preferable minimum is 2 micrometers and a preferable upper limit is 200 micrometers.
  • a preferable minimum is 2 micrometers and a preferable upper limit is 200 micrometers.
  • the thickness of the base material is less than 2 ⁇ m, the strength of the obtained pressure-sensitive adhesive tape for optical members is insufficient, and it may be torn or difficult to handle.
  • the thickness of the base material exceeds 200 ⁇ m, the base material is too strong, and the followability to the step of the obtained pressure-sensitive adhesive tape for optical members may be deteriorated.
  • a more preferable lower limit of the thickness of the substrate is 5 ⁇ m, and a more preferable upper limit is 100 ⁇ m.
  • the method for producing the pressure-sensitive adhesive tape for optical members of the present invention is not particularly limited.
  • the pressure-sensitive adhesive layer is formed by coating the pressure-sensitive adhesive composition for optical members of the present invention on the release paper or release film of the release film. Then, on the obtained pressure-sensitive adhesive layer, a newly prepared release paper or release film with a release treatment surface in contact with the pressure-sensitive adhesive layer was overlaid to obtain a laminate, and then the obtained laminate Examples include a method of pressing the body with a rubber roller or the like.
  • the monomer having the hydrophilic group, the monomer having the bicyclo ring structure and one olefinic double bond, which are blended as necessary, etc. A method in which a mixed monomer containing other monomers is radically polymerized by bulk polymerization to produce the above acrylic copolymer and at the same time to tape formation at a stretch is suitably used.
  • the bulk polymerization is preferably photopolymerization because the heat of polymerization is easily removed and the reaction is easily controlled.
  • a monomer composition containing the above-mentioned mixed monomer, photopolymerization initiator, and, if necessary, an additive and the like and containing no solvent After forming the monomer layer by coating on the release treatment surface of the transparent synthetic resin film whose surface was release-treated, another transparent composition with one surface being release-treated on this monomer layer A method in which the mixed monomer is radically polymerized by superimposing the release treatment surfaces of the resin film and irradiating the monomer layer with light such as ultraviolet irradiation through the synthetic resin film is preferably used.
  • the pressure-sensitive adhesive tape for optical members of the present invention is produced by photopolymerization, a cross-linked structure can be formed simultaneously with the polymerization, so the mixed monomer is a polyfunctional (meth) acrylate having two or more polymerizable functional groups. It is preferable to contain.
  • the polyfunctional (meth) acrylate is not particularly limited.
  • examples include di (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyurethane di (meth) acrylate, and polyester di (meth) acrylate.
  • 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, hydrogenated polybutadiene diacrylate, polyurethane diacrylate, and polyester diacrylate are preferred because the pressure dispersion of the resulting pressure-sensitive adhesive layer is small and excellent in adhesive performance. Is preferred.
  • the compounding quantity of the said polyfunctional (meth) acrylate is not specifically limited, The preferable minimum in the said mixed monomer is 0.02 weight%, A preferable upper limit is 5 % By weight.
  • the blending amount of the polyfunctional (meth) acrylate is less than 0.02% by weight, the acrylic copolymer is insufficiently cross-linked, and the resulting pressure-sensitive adhesive layer has reduced cohesion and processability. There are things to do.
  • the blending amount of the polyfunctional (meth) acrylate is more than 5% by weight, the pressure-sensitive adhesive layer obtained may have reduced adhesive strength and initial adhesiveness to the adherend, resulting in reduced reliability.
  • the compounding quantity of the said polyfunctional (meth) acrylate the more preferable minimum in the said mixed monomer is 0.05 weight%, and a more preferable upper limit is 3 weight%.
  • the photopolymerization initiator is not particularly limited, and examples thereof include ketone photopolymerization such as 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (trade name “Darocur 2959” manufactured by Merck).
  • Initiator ⁇ -hydroxy- ⁇ , ⁇ '-dimethyl-acetophenone (Merck, trade name “Darocur 1173”), methoxyacetophene, 2,2-dimethoxy-2-phenylacetophene (Ciba Geigy, trade name) "Irgacure 651”), 2-hydroxy-2-cyclohexyl acetophenone (product name "Irgacure 184" manufactured by Ciba Geigy Co., Ltd.), etc., ketal photopolymerization initiators such as benzyldimethyl ketal, halogenated ketones , Acyl phosphinoxide, acyl phosphonate and the like.
  • the preferable minimum with respect to 100 weight part of said mixed monomers is 0.01 weight part, and a preferable upper limit is 5 weight part.
  • a preferable upper limit is 5 weight part.
  • the blending amount of the photopolymerization initiator is less than 0.01 parts by weight, the polymerization of the mixed monomer becomes incomplete, and the obtained pressure-sensitive adhesive layer has the necessary physical properties due to a decrease in cohesive force. It may not be possible. If the blending amount of the photopolymerization initiator exceeds 5 parts by weight, the amount of radicals generated during light irradiation increases, the number average molecular weight of the resulting acrylic copolymer decreases, or the gel fraction of the pressure-sensitive adhesive layer decreases.
  • the more preferable minimum with respect to 100 weight part of said mixed monomers is 0.03 weight part, and a more preferable upper limit is 1 weight part.
  • the said transparent synthetic resin film is not specifically limited, For example, a polyethylene terephthalate film etc. are mentioned.
  • the lamp used for the light irradiation is not particularly limited, and examples thereof include a lamp having a light emission distribution at a wavelength of 400 nm or less.
  • Examples of the lamp having a light emission distribution at a wavelength of 400 nm or less include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp. It is done. Among these, the light in the active wavelength region of the photopolymerization initiator is efficiently emitted, and there is little light absorption of components other than the photopolymerization initiator contained in the monomer layer, so that light can enter the monomer layer.
  • a chemical lamp is preferred because it can sufficiently reach and effectively polymerize the mixed monomer.
  • the light irradiation intensity in the above light irradiation is not particularly limited, and is a factor that affects the degree of polymerization of the resulting acrylic copolymer, so that it matches the degree of polymerization of the target acrylic copolymer or the performance of the pressure-sensitive adhesive layer. And adjusted as appropriate.
  • the light irradiation intensity in the wavelength region effective for photolysis of the acetophenone photopolymerization initiator is 0.1 to 100 mW / cm 2 . It is preferable.
  • the wavelength range effective for the photodecomposition of the acetophenone-based photopolymerization initiator is usually about 365 nm to 420 nm, although it varies depending on the photopolymerization initiator.
  • the application of the pressure-sensitive adhesive tape for optical members of the present invention is not particularly limited, and can be applied to various optical members.
  • the pressure-sensitive adhesive tape for optical members of the present invention is used in the manufacture of image display devices such as mobile phones and portable information terminals. Used to attach a protective plate for protecting the surface and a display panel, or when manufacturing an input device such as a mobile phone or a portable information terminal, a polycarbonate plate or an acrylic plate of a touch panel, and a display panel It is preferable to use for bonding together.
  • the whitening which arises under high temperature and high humidity can be suppressed, and the adhesive composition for optical members which can implement
  • the adhesive tape for optical members manufactured using this adhesive composition for optical members can be provided.
  • Example 1-1 Production of acrylic copolymer In a reactor equipped with a thermometer, a stirrer, and a cooling tube, 44.5 parts by weight of 2-ethylhexyl acrylate, 30 parts by weight of isobornyl acrylate, and 0.5 parts by weight of acrylic acid Then, 25 parts by weight of 2-hydroxyethyl acrylate, and 100 parts by weight of ethyl acetate with respect to 100 parts by weight of these monomers were replaced with nitrogen, and then the reactor was heated to start refluxing.
  • Examples 1-2 to 1-5 Comparative Examples 1-1 to 1-3
  • the mold release was carried out in the same manner as in Example 1-1, except that the acrylic copolymer having the proportion (% by weight) shown in Table 1 was obtained by changing the monomer composition of the acrylic copolymer.
  • a double-sided pressure-sensitive adhesive tape for an optical member having a polyethylene terephthalate film attached on both sides was obtained.
  • Example 2-1 Production of acrylic copolymer In a reactor equipped with a thermometer, a stirrer, and a cooling tube, 59.5 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of isobornyl acrylate, and 0.5 parts by weight of acrylic acid And 25 parts by weight of N-vinylpyrrolidone and 100 parts by weight of ethyl acetate with respect to 100 parts by weight of these monomers were substituted by nitrogen bubbling, and then the reactor was brought to 70 ° C. under a nitrogen flow.
  • 0.2 parts by weight of t-hexylperoxypivalate as a polymerization initiator is diluted with 5 parts by weight of ethyl acetate with respect to 100 parts by weight of the monomer, and the resulting polymerization initiator solution is diluted with the above reactor.
  • the solution was added dropwise over 2 hours.
  • the temperature was controlled by heating and cooling so that the reaction temperature was maintained at 70 ° C.
  • the reaction was carried out at 70 ° C. for 8 hours from the start of the addition of the polymerization initiator, and then the reaction was terminated by cooling to obtain an acrylic copolymer solution having a solid content of 50%.
  • Examples 2-2 to 2-8 Comparative Examples 2-1 to 2-3
  • the acrylic copolymer having the proportion (% by weight) of the structural units and the weight average molecular weight shown in Table 2 was obtained.
  • a double-sided pressure-sensitive adhesive tape for an optical member having a release polyethylene terephthalate film attached on both sides was obtained.
  • the weight average molecular weight by polystyrene conversion was measured by GPC method using "2690 Separations Model" made from Waters as a column.
  • the obtained weight average molecular weight is shown in Table 3.
  • Examples 3-2 to 3-9 Comparative Examples 3-1 to 3-5
  • the acrylic copolymer having the weight average molecular weight shown in Table 3 or 4 was obtained by changing the monomer composition of the acrylic copolymer as shown in Table 3 or 4.
  • a double-sided pressure-sensitive adhesive tape for optical members having a release polyethylene terephthalate film attached on both sides was obtained.
  • a monomer composition from which dissolved oxygen was removed was produced by uniformly purging with a product name “Irgacure 651” manufactured by the company, and then purging with nitrogen.
  • the obtained monomer composition was sandwiched between two silicon release polyethylene terephthalate films having a thickness of 38 ⁇ m through two spacers having a thickness of 100 ⁇ m so that the thickness would be 100 ⁇ m so that each release treatment surface was in contact with the monomer composition. It is.
  • a double-sided pressure-sensitive adhesive tape for an optical member having a release polyethylene terephthalate film attached to both sides is obtained by polymerizing the monomer by irradiating the monomer composition with 2 mW ultraviolet rays for 5 minutes using a fluorescent lamp having a dominant wavelength of 365 nm. Obtained.
  • Examples 3-11 to 3-18, Comparative Examples 3-6 to 3-10) A release polyethylene terephthalate film was applied to both sides in the same manner as in Example 3-10, except that the acrylic copolymer was obtained by changing the monomer composition of the acrylic copolymer as shown in Table 5 or 6. The obtained double-sided pressure-sensitive adhesive tape for optical members was obtained.
  • the weight average molecular weight by polystyrene conversion was measured by GPC method using "2690 Separations Model" made from Waters as a column.
  • the obtained weight average molecular weight is shown in Table 7.
  • Examples 4-2 to 4-9 Comparative Example 4-1
  • the acrylic copolymer having the weight average molecular weight shown in Table 7 was obtained by changing the monomer composition of the acrylic copolymer as shown in Table 7.
  • a double-sided pressure-sensitive adhesive tape for optical members having a polyethylene terephthalate film attached on both sides was obtained.
  • a monomer composition from which dissolved oxygen was removed was produced by uniformly purging with a product name “Irgacure 651” manufactured by the company, and then purging with nitrogen.
  • the obtained monomer composition was sandwiched between two silicon release polyethylene terephthalate films having a thickness of 38 ⁇ m through two spacers having a thickness of 100 ⁇ m so that the thickness would be 100 ⁇ m so that each release treatment surface was in contact with the monomer composition. It is.
  • a double-sided pressure-sensitive adhesive tape for an optical member having a release polyethylene terephthalate film attached to both sides is obtained by polymerizing the monomer by irradiating the monomer composition with 2 mW ultraviolet rays for 5 minutes using a fluorescent lamp having a dominant wavelength of 365 nm. Obtained.
  • Example 4-11 to 4-18 Comparative Example 4-2
  • a release polyethylene terephthalate film was attached to both sides in the same manner as in Example 4-10, except that the acrylic copolymer was obtained by changing the monomer composition of the acrylic copolymer as shown in Table 8.
  • a double-sided pressure-sensitive adhesive tape for optical members was obtained.
  • ⁇ haze value ⁇ haze value of test piece after standing for 24 hours (%) ⁇ ⁇ ⁇ haze value immediately after preparation of test piece (%) ⁇ (2)
  • the obtained double-sided adhesive tape for optical members was cut so as to have a planar shape of 25 mm ⁇ 100 mm.
  • One release polyethylene terephthalate film of the cut double-sided pressure-sensitive adhesive tape for optical members was peeled, and the exposed surface of the double-sided pressure-sensitive adhesive tape for optical members was bonded onto the polyethylene terephthalate film.
  • the other release polyethylene terephthalate film of the double-sided pressure-sensitive adhesive tape for optical members is peeled off, and the exposed surface of the double-sided pressure-sensitive adhesive tape for optical members is bonded onto the polycarbonate plate (PC plate), whereby a polycarbonate plate (PC plate) )
  • PC plate polycarbonate plate
  • a 2.0 kg rubber roller is placed on the polyethylene terephthalate film of the obtained laminated sample, and the rubber roller is reciprocated once at a speed of 300 mm / min. And left at 23 ° C. for 20 minutes to prepare a test sample.
  • the obtained test sample was subjected to a tensile test in the 180 ° direction at a peeling speed of 300 mm / min according to JIS Z0237, and the initial adhesive strength (N / 25 mm) was measured.
  • the obtained test sample was allowed to stand at 23 ° C. for 24 hours, and then subjected to a tensile test in the 180 ° direction at a peeling rate of 300 mm / min according to JIS Z0237, and the adhesive strength (N / 25 mm) after 24 hours was measured. It was measured.
  • the obtained double-sided pressure-sensitive adhesive tape for optical members was cut so as to have a flat shape of 45 mm ⁇ 60 mm.
  • One release polyethylene terephthalate film of the cut double-sided pressure-sensitive adhesive tape for optical members was peeled, and the exposed surface of the double-sided pressure-sensitive adhesive tape for optical members was bonded onto a polyethylene terephthalate film having a thickness of 0.5 mm.
  • the other release polyethylene terephthalate film of the double-sided pressure-sensitive adhesive tape for optical members is peeled, and the exposed surface of the double-sided pressure-sensitive adhesive tape for optical members is placed on a polycarbonate plate (PC plate) having a planar shape with a thickness of 2.0 mm.
  • PC plate polycarbonate plate
  • a laminated sample in which a double-sided pressure-sensitive adhesive tape for optical members and a polyethylene terephthalate film were laminated in this order on a polycarbonate plate (PC plate) was obtained. Thereafter, the obtained laminated sample was allowed to stand for 24 hours under the condition of a temperature of 85 ° C. or a temperature of 60 ° C. and a relative humidity (RH) of 90% to obtain a test sample.
  • the bubble generation state in the adhesion interface of the obtained test sample was visually observed. “ ⁇ ” indicates that no bubbles having a size of 0.01 mm or more were observed, and “ ⁇ ” indicates that 1 to 5 bubbles having a size of 0.01 mm or more were observed per test sample.
  • the bubble generation state was evaluated by setting “x” when 6 or more bubbles having a size of 0.01 mm or more were observed per test sample.
  • the obtained double-sided pressure-sensitive adhesive tape for optical members was cut so as to have a planar shape of length 40 mm ⁇ width 60 mm. Further, two corners adjacent in the width direction were cut into a planar shape having a length of 10 mm from the corner and a width of 10 mm from the corner to obtain a convex tape sheet.
  • One release polyethylene terephthalate film of the convex tape sheet was peeled off, and the exposed surface of the convex tape sheet was bonded onto polyethylene terephthalate.
  • the other release polyethylene terephthalate film of the convex tape sheet is peeled off, and the exposed surface of the convex tape sheet is pasted on the ITO film surface of the ITO film having a planar shape of length 40 mm ⁇ width 60 mm.
  • the conductive film laminated body by which the double-sided adhesive tape for optical members and the polyethylene terephthalate were laminated
  • Resistance value change rate (%) (R 1 ⁇ R 0 ) / R 0 ⁇ 100 (3)
  • R 0 represents an initial resistance value
  • R 1 represents a resistance value after being left for 100 hours under high temperature and high humidity.
  • the resistance value change rate is preferably 20% or less, and more preferably 15% or less. If the resistance value change rate exceeds 20%, an erroneous electric signal may be input to the recognition part of the touch panel having the ITO film, which may cause a bad response.
  • the whitening which arises under high temperature and high humidity can be suppressed, and the adhesive composition for optical members which can implement
  • the adhesive tape for optical members manufactured using this adhesive composition for optical members can be provided.

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Abstract

Provided is a pressure-sensitive adhesive composition for optical members which is protected from whitening under high -temperature and high-humidity conditions and which can ensure high reliability. Also provided is a pressure-sensitive adhesive tape for optical members, which is produced using the pressure-sensitive adhesive composition. The pressure -sensitive adhesive composition for optical members comprises an acrylic copolymer obtained by polymerizing a mixed monomer which contains 1 to 25wt% of 2-hydroxyethyl acrylate, 1 to 25wt% of N-vinylpyrrolidone, 0.5 to 30wt% of a monomer having a structure represented by general formula (1-1), or 0.1 to 30wt% of a monomer having a structure represented by general formula (1-2). In general formula (1-1), R1 is hydrogen or methyl; R2 is hydrogen or alkyl having less than 3 carbon atoms; and n is an integer of 8 to 45. In general formula (1-2), R3 is hydrogen or methyl; R4 is alkyl having 3 to 30 carbon atoms; and m is an integer of 8 to 45.

Description

光学部材用粘着剤組成物及び光学部材用粘着テープOptical member pressure-sensitive adhesive composition and optical member pressure-sensitive adhesive tape
本発明は、高温高湿下で生じる白化を抑制し、高信頼性を実現することのできる光学部材用粘着剤組成物に関する。また、本発明は、該光学部材用粘着剤組成物を用いて製造される光学部材用粘着テープに関する。 The present invention relates to a pressure-sensitive adhesive composition for an optical member that can suppress whitening that occurs under high temperature and high humidity and realize high reliability. Moreover, this invention relates to the adhesive tape for optical members manufactured using this adhesive composition for optical members.
ディスプレイパネルは様々な分野で用いられており、特に携帯電話、携帯情報端末等においては、画像表示装置だけではなく入力装置にも用いられている。このような画像表示装置又は入力装置において、ディスプレイパネルは、例えばアクリル系粘着剤等の透明性の高い粘着剤又は粘着テープによって、表面を保護する保護板、タッチパネル又は光学フィルター等に貼り合わされている。 Display panels are used in various fields, and particularly in mobile phones, personal digital assistants, etc., they are used not only for image display devices but also for input devices. In such an image display device or input device, the display panel is bonded to a protective plate, a touch panel, an optical filter, or the like that protects the surface with a highly transparent adhesive such as an acrylic adhesive or an adhesive tape. .
しかしながら、従来、アクリル系粘着剤は、高温高湿下に曝された後室温に戻されると、吸湿した水分が結露することによって白化し、視認性の低下をもたらすことが問題となっている。このような白化による視認性の低下は、画像表示装置又は入力装置にとっては致命的な欠陥となりうる。 However, conventionally, when an acrylic pressure-sensitive adhesive is returned to room temperature after being exposed to high temperature and high humidity, it has been a problem that moisture that has been absorbed whitens due to condensation, resulting in a decrease in visibility. Such a decrease in visibility due to whitening can be a fatal defect for an image display device or an input device.
この問題に対し、例えば、特許文献1には、アクリル酸エステル及びメタクリル酸エステルからなるABA型トリブロック共重合体と、水酸基を有する樹脂とをポリマーブレンドしてなるアクリル系透明粘着剤組成物が開示されている。特許文献1には、同文献に記載のアクリル系透明粘着剤組成物は、高温多湿環境、温水浸漬環境、煮沸環境等の環境下に長時間曝されても、白化することがなく透明性を維持することができると記載されている。 For this problem, for example, Patent Document 1 discloses an acrylic transparent pressure-sensitive adhesive composition obtained by polymer blending an ABA triblock copolymer composed of an acrylic ester and a methacrylic ester and a resin having a hydroxyl group. It is disclosed. In Patent Document 1, the acrylic transparent pressure-sensitive adhesive composition described in the same document has transparency without whitening even when exposed to an environment such as a high-temperature and high-humidity environment, a hot-water immersion environment, or a boiling environment for a long time. It is stated that it can be maintained.
しかしながら、特許文献1に記載のアクリル系透明粘着剤組成物は、ブレンドされる水酸基を有する樹脂が低分子量であることから、粘着剤又は粘着テープに本来必要とされる粘着物性、耐熱性等の面で充分とはいえない。従って、粘着剤又は粘着テープとしての信頼性を低下させることなく、同時に高温高湿下で生じる白化を抑制することのできる新たな粘着剤又は粘着テープが求められている。 However, the acrylic transparent pressure-sensitive adhesive composition described in Patent Document 1 has a low molecular weight resin having a hydroxyl group to be blended, and therefore has such properties as pressure-sensitive adhesive properties and heat resistance that are originally required for a pressure-sensitive adhesive or pressure-sensitive adhesive tape. It ’s not enough. Accordingly, there is a need for a new pressure-sensitive adhesive or pressure-sensitive adhesive tape that can simultaneously suppress whitening that occurs under high temperature and high humidity without reducing the reliability of the pressure-sensitive adhesive or pressure-sensitive adhesive tape.
特開2009-102467号公報JP 2009-102467 A
本発明は、高温高湿下で生じる白化を抑制し、高信頼性を実現することのできる光学部材用粘着剤組成物を提供することを目的とする。また、本発明は、該光学部材用粘着剤組成物を用いて製造される光学部材用粘着テープを提供することを目的とする。 An object of this invention is to provide the adhesive composition for optical members which can suppress the whitening which arises under high temperature, high humidity, and can implement | achieve high reliability. Moreover, an object of this invention is to provide the adhesive tape for optical members manufactured using this adhesive composition for optical members.
本発明は、アクリル共重合体を含有する光学部材用粘着剤組成物であって、前記アクリル共重合体は、2-ヒドロキシエチルアクリレート1~25重量%、N-ビニルピロリドン1~25重量%、下記一般式(1-1)で表される構造を有するモノマー0.5~30重量%、又は、下記一般式(1-2)で表される構造を有するモノマー0.1~30重量%を含有する混合モノマーを重合することにより得られる光学部材用粘着剤組成物である。 The present invention is an adhesive composition for an optical member containing an acrylic copolymer, the acrylic copolymer comprising 1 to 25% by weight of 2-hydroxyethyl acrylate, 1 to 25% by weight of N-vinylpyrrolidone, 0.5 to 30% by weight of a monomer having a structure represented by the following general formula (1-1), or 0.1 to 30% by weight of a monomer having a structure represented by the following general formula (1-2) It is the adhesive composition for optical members obtained by superposing | polymerizing the mixed monomer to contain.
Figure JPOXMLDOC01-appb-C000004
一般式(1-1)中、Rは水素原子又はメチル基を表し、Rは水素原子又は炭素数3未満のアルキル基を表し、nは8~45の整数を表す。
Figure JPOXMLDOC01-appb-C000004
In general formula (1-1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or an alkyl group having less than 3 carbon atoms, and n represents an integer of 8 to 45.
Figure JPOXMLDOC01-appb-C000005
一般式(1-2)中、Rは水素原子又はメチル基を表し、Rは炭素数3~30のアルキル基を表し、mは8~45の整数を表す。
以下、本発明を詳述する。
Figure JPOXMLDOC01-appb-C000005
In general formula (1-2), R 3 represents a hydrogen atom or a methyl group, R 4 represents an alkyl group having 3 to 30 carbon atoms, and m represents an integer of 8 to 45.
The present invention is described in detail below.
本発明者らは、アクリル共重合体を含有する光学部材用粘着剤組成物において、アクリル共重合体を構成するモノマーに高親水性モノマーを用いることにより、高温高湿下に曝された後室温に戻された場合に水を微分散させ、その結果、白化を抑制することができることを見出した。
本発明者らは、高親水性モノマーの多くはアクリル共重合体のガラス転移温度(Tg)を必要以上に上昇させてしまい、粘着剤組成物に適さないのに対し、2-ヒドロキシエチルアクリレート、N-ビニルピロリドン、又は、ポリエチレンオキサイド鎖を有する特定のモノマーを所定の割合で用いることにより、高温高湿下で生じる白化を抑制することができ、かつ、高信頼性を実現することのできる光学部材用粘着剤組成物が得られることを見出し、本発明を完成させるに至った。
In the pressure-sensitive adhesive composition for an optical member containing an acrylic copolymer, the present inventors use a highly hydrophilic monomer as a monomer constituting the acrylic copolymer, so that it is exposed to room temperature after being exposed to high temperature and high humidity. It was found that water was finely dispersed when it was returned to, and as a result, whitening could be suppressed.
The present inventors have found that many of the highly hydrophilic monomers increase the glass transition temperature (Tg) of the acrylic copolymer more than necessary and are not suitable for the pressure-sensitive adhesive composition, whereas 2-hydroxyethyl acrylate, By using N-vinylpyrrolidone or a specific monomer having a polyethylene oxide chain at a predetermined ratio, whitening that occurs under high temperature and high humidity can be suppressed, and high reliability can be realized. It discovered that the adhesive composition for members was obtained, and came to complete this invention.
本発明の光学部材用粘着剤組成物は、アクリル共重合体を含有する。
上記アクリル共重合体は、2-ヒドロキシエチルアクリレート1~25重量%、N-ビニルピロリドン1~25重量%、下記一般式(1-1)で表される構造を有するモノマー0.5~30重量%、又は、下記一般式(1-2)で表される構造を有するモノマー0.1~30重量%を含有する混合モノマーを重合することにより得られる。
The pressure-sensitive adhesive composition for optical members of the present invention contains an acrylic copolymer.
The acrylic copolymer is composed of 1 to 25% by weight of 2-hydroxyethyl acrylate, 1 to 25% by weight of N-vinylpyrrolidone, and 0.5 to 30% by weight of a monomer having a structure represented by the following general formula (1-1) %, Or a mixed monomer containing 0.1 to 30% by weight of a monomer having a structure represented by the following general formula (1-2).
Figure JPOXMLDOC01-appb-C000006
一般式(1-1)中、Rは水素原子又はメチル基を表し、Rは水素原子又は炭素数3未満のアルキル基を表し、nは8~45の整数を表す。
Figure JPOXMLDOC01-appb-C000006
In general formula (1-1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or an alkyl group having less than 3 carbon atoms, and n represents an integer of 8 to 45.
Figure JPOXMLDOC01-appb-C000007
一般式(1-2)中、Rは水素原子又はメチル基を表し、Rは炭素数3~30のアルキル基を表し、mは8~45の整数を表す。
Figure JPOXMLDOC01-appb-C000007
In general formula (1-2), R 3 represents a hydrogen atom or a methyl group, R 4 represents an alkyl group having 3 to 30 carbon atoms, and m represents an integer of 8 to 45.
2-ヒドロキシエチルアクリレート、N-ビニルピロリドン、上記一般式(1-1)で表される構造を有するモノマー、及び、上記一般式(1-2)で表される構造を有するモノマーは親水性基を有し、親水性が高い。そのため、上記混合モノマーが上記範囲の割合でこれらのモノマーを含有することにより、本発明の光学部材用粘着剤組成物は、高温高湿下に曝された後室温に戻された場合に水を微分散させ、その結果、白化を抑制することができる。
本明細書中、2-ヒドロキシエチルアクリレート、N-ビニルピロリドン、上記一般式(1-1)で表される構造を有するモノマー、及び、上記一般式(1-2)で表される構造を有するモノマーを「親水性基を有するモノマー」ともいう。
また、上記親水性基を有するモノマーは、上記アクリル共重合体のガラス転移温度(Tg)を必要以上に上昇させることがなく、本発明の光学部材用粘着剤組成物の信頼性に悪影響を及ぼすこともない。
また、通常、ITO等の金属又は金属酸化物を含有する金属薄膜を被着体とした場合にアクリル系粘着剤の白化は顕著となるが、上記混合モノマーが上記範囲の割合で上記親水性基を有するモノマーを含有することにより、本発明の光学部材用粘着剤組成物は、ITO等の金属又は金属酸化物を含有する金属薄膜を被着体とした場合にも高温高湿下で生じる白化を抑制することができる。
2-hydroxyethyl acrylate, N-vinylpyrrolidone, a monomer having a structure represented by the general formula (1-1), and a monomer having a structure represented by the general formula (1-2) are hydrophilic groups. And has high hydrophilicity. Therefore, when the above-mentioned mixed monomer contains these monomers in a proportion within the above range, the pressure-sensitive adhesive composition for an optical member of the present invention can absorb water when it is returned to room temperature after being exposed to high temperature and high humidity. Fine dispersion is achieved, and as a result, whitening can be suppressed.
In the present specification, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, a monomer having a structure represented by the above general formula (1-1), and a structure represented by the above general formula (1-2) The monomer is also referred to as “monomer having a hydrophilic group”.
Further, the monomer having a hydrophilic group does not unnecessarily increase the glass transition temperature (Tg) of the acrylic copolymer, and adversely affects the reliability of the pressure-sensitive adhesive composition for optical members of the present invention. There is nothing.
In general, when a metal thin film containing a metal such as ITO or a metal oxide is used as an adherend, the whitening of the acrylic pressure-sensitive adhesive becomes remarkable, but the above-mentioned mixed monomer is in the above-mentioned range in the above-mentioned hydrophilic group. The adhesive composition for optical members of the present invention contains a monomer having a whitening that occurs under high temperature and high humidity even when a metal thin film containing a metal or metal oxide such as ITO is used as an adherend. Can be suppressed.
なお、上記親水性基を有するモノマーのほかにも、白化を抑制する効果を有し、かつ、信頼性に悪影響を及ぼすことのない高親水性モノマーとして、例えば、4-ヒドロキシブチルアクリレート(4-HBA)、3-ヒドロキシプロピルアクリレート(3-HPA)、6-ヒドロキシヘキシルアクリレート(6-HHA)等が挙げられる。上記混合モノマーは、これらの高親水性モノマーを含有してもよい。 In addition to the above-mentioned monomer having a hydrophilic group, as a highly hydrophilic monomer that has an effect of suppressing whitening and does not adversely affect reliability, for example, 4-hydroxybutyl acrylate (4- HBA), 3-hydroxypropyl acrylate (3-HPA), 6-hydroxyhexyl acrylate (6-HHA) and the like. The mixed monomer may contain these highly hydrophilic monomers.
上記親水性基を有するモノマーのなかでも、初期接着性が高く、かつ、時間が経過しても高い接着性を維持できる光学部材用粘着剤組成物が得られ、更に、ITO等の金属又は金属酸化物を含有する金属薄膜を被着体とした場合に高温高湿下で生じる白化をより効果的に抑制することができることから、上記一般式(1-1)で表される構造を有するモノマー、又は、上記一般式(1-2)で表される構造を有するモノマーが好ましい。
また、本発明の光学部材用粘着剤組成物が後述するような架橋剤を含有する場合には、上記親水性基を有するモノマーが2-ヒドロキシエチルアクリレート又はN-ビニルピロリドンであると、架橋剤の種類又は量によっては光学部材用粘着剤組成物のゲル化が急激に進行してしまい、取扱性が低下することがある。従って、架橋剤の種類及び量を充分制御する必要がある。これに対し、上記親水性基を有するモノマーが上記一般式(1-1)で表される構造を有するモノマー、又は、上記一般式(1-2)で表される構造を有するモノマーであることで、架橋剤の種類又は量によって光学部材用粘着剤組成物のゲル化が急激に進行することを抑制することができ、架橋剤の種類及び量の制御が容易となる。
Among the above-mentioned monomers having a hydrophilic group, a pressure-sensitive adhesive composition for an optical member having high initial adhesiveness and capable of maintaining high adhesiveness even after time has been obtained, and further, a metal such as ITO or a metal A monomer having a structure represented by the above general formula (1-1) can be more effectively suppressed whitening that occurs under high temperature and high humidity when a metal thin film containing an oxide is used as an adherend. Alternatively, a monomer having a structure represented by the general formula (1-2) is preferable.
In the case where the pressure-sensitive adhesive composition for an optical member of the present invention contains a crosslinking agent as described later, the monomer having the hydrophilic group is 2-hydroxyethyl acrylate or N-vinylpyrrolidone. Depending on the type or amount, gelation of the pressure-sensitive adhesive composition for optical members may proceed rapidly, and the handleability may deteriorate. Therefore, it is necessary to sufficiently control the type and amount of the crosslinking agent. In contrast, the monomer having a hydrophilic group is a monomer having a structure represented by the general formula (1-1) or a monomer having a structure represented by the general formula (1-2). Therefore, it is possible to prevent the gelation of the pressure-sensitive adhesive composition for optical members from proceeding rapidly depending on the type or amount of the crosslinking agent, and the type and amount of the crosslinking agent can be easily controlled.
上記一般式(1-1)で表される構造を有するモノマー、及び、上記一般式(1-2)で表される構造を有するモノマーにおいて、エチレンオキサイドの繰り返し数は、下限が8、上限が45である。上記エチレンオキサイドの繰り返し数が8未満であると、得られる光学部材用粘着剤組成物は、高温高湿下で生じる白化を充分に抑制することができない。上記エチレンオキサイドの繰り返し数が45を超えると、得られる光学部材用粘着剤組成物は、高温高湿下で生じる白化を充分に抑制することができない。また、上記エチレンオキサイドの繰り返し数が45を超えると、上記一般式(1-1)で表される構造を有するモノマー、又は、上記一般式(1-2)で表される構造を有するモノマーと他の主成分となるモノマー等との相溶性が低下し、得られる光学部材用粘着剤組成物は、粘着力が低下する。
上記エチレンオキサイドの繰り返し数は、高温高湿下で生じる白化をより効果的に抑制することができることから、好ましい下限が13、好ましい上限が40である。上記エチレンオキサイドの繰り返し数は、30であることが特に好ましい。なお、上記エチレンオキサイドの繰り返し数は、上記一般式(1-1)においてはnで表され、上記一般式(1-2)においてはmで表される。
In the monomer having the structure represented by the general formula (1-1) and the monomer having the structure represented by the general formula (1-2), the number of ethylene oxide repeats is 8 for the lower limit and 8 for the upper limit. 45. When the number of ethylene oxide repeats is less than 8, the resulting pressure-sensitive adhesive composition for optical members cannot sufficiently suppress whitening that occurs under high temperature and high humidity. When the number of ethylene oxide repeats exceeds 45, the resulting pressure-sensitive adhesive composition for optical members cannot sufficiently suppress whitening that occurs under high temperature and high humidity. When the ethylene oxide repeat number exceeds 45, a monomer having a structure represented by the general formula (1-1) or a monomer having a structure represented by the general formula (1-2) Compatibility with other main components such as monomers decreases, and the resulting pressure-sensitive adhesive composition for optical members has reduced adhesive strength.
Since the repetition number of the ethylene oxide can more effectively suppress whitening that occurs under high temperature and high humidity, the preferable lower limit is 13 and the preferable upper limit is 40. The number of ethylene oxide repeats is particularly preferably 30. The repeating number of ethylene oxide is represented by n in the general formula (1-1) and represented by m in the general formula (1-2).
上記一般式(1-1)で表される構造を有するモノマーにおいて、ポリエチレンオキサイド鎖の末端基は水素原子又は炭素数3未満のアルキル基である。なかでも、より高温高湿の条件でも白化を抑制することのできる光学部材用粘着剤組成物が得られることから、炭素数3未満のアルキル基が好ましい。
なお、上記ポリエチレンオキサイド鎖の末端基は、上記一般式(1-1)においてはRで表される。
In the monomer having the structure represented by the general formula (1-1), the terminal group of the polyethylene oxide chain is a hydrogen atom or an alkyl group having less than 3 carbon atoms. Especially, since the adhesive composition for optical members which can suppress whitening also on conditions of higher temperature and humidity is obtained, an alkyl group with less than 3 carbon atoms is preferable.
The terminal group of the polyethylene oxide chain is represented by R 2 in the general formula (1-1).
上記一般式(1-2)で表される構造を有するモノマーにおいて、ポリエチレンオキサイド鎖の末端基は炭素数3~30のアルキル基である。上記ポリエチレンオキサイド鎖の末端基は、より高温高湿の条件でも白化を抑制することのできる光学部材用粘着剤組成物が得られることから、炭素数18のアルキル基であることが好ましい。なお、上記ポリエチレンオキサイド鎖の末端基は、上記一般式(1-2)においてはRで表される。 In the monomer having the structure represented by the general formula (1-2), the end group of the polyethylene oxide chain is an alkyl group having 3 to 30 carbon atoms. The terminal group of the polyethylene oxide chain is preferably an alkyl group having 18 carbon atoms because a pressure-sensitive adhesive composition for an optical member that can suppress whitening even under conditions of higher temperature and higher humidity is obtained. The end group of the polyethylene oxide chain is represented by R 4 in the general formula (1-2).
上記一般式(1-1)で表される構造を有するモノマー、又は、上記一般式(1-2)で表される構造を有するモノマーのうち、市販品として、例えば、ブレンマーPME-1000(エチレンオキサイドの繰り返し数=23、末端メチル基、日油社製)、ブレンマーPME-400(エチレンオキサイドの繰り返し数=9、末端メチル基、日油社製)、ブレンマーPME-2000(エチレンオキサイドの繰り返し数=45、末端メチル基、日油社製)、NKエステルAM-130G(エチレンオキサイドの繰り返し数=13、末端メチル基、新中村化学工業社製)、ライトエステル041MA(エチレンオキサイドの繰り返し数=30、末端メチル基、共栄社化学社製)、ブレンマーPSE-1300(エチレンオキサイドの繰り返し数=30、末端オクタデシル基、日油社製)、ブレンマーAE-400(エチレンオキサイドの繰り返し数=10、末端水酸基、日油社製)、ブレンマーANE-1300(エチレンオキサイドの繰り返し数=30、末端ノニルフェニル基、日油社製)等が挙げられる。 Among the monomers having the structure represented by the general formula (1-1) or the monomers having the structure represented by the general formula (1-2), commercially available products such as Blemmer PME-1000 (ethylene Oxide repeat number = 23, terminal methyl group, manufactured by NOF Corporation), BLEMMER PME-400 (ethylene oxide repeat number = 9, terminal methyl group, manufactured by NOF Corporation), BLEMMER PME-2000 (ethylene oxide repeat number) = 45, terminal methyl group, manufactured by NOF Corporation), NK ester AM-130G (ethylene oxide repeat number = 13, terminal methyl group, manufactured by Shin-Nakamura Chemical Co., Ltd.), light ester 041MA (ethylene oxide repeat number = 30) , Terminal methyl group, manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PSE-1300 (repetition number of ethylene oxide 30, terminal octadecyl group (manufactured by NOF Corporation), BLEMMER AE-400 (ethylene oxide repeat number = 10, terminal hydroxyl group, NOF Corporation), BLEMMER AE-1300 (ethylene oxide repeat number = 30, terminal nonylphenyl) Group, manufactured by NOF Corporation).
上記混合モノマーにおける上記親水性基を有するモノマーの割合が少なすぎると、得られる光学部材用粘着剤組成物は、高温高湿下で生じる白化を充分に抑制することができない。上記混合モノマーにおける上記親水性基を有するモノマーの割合が多すぎると、得られる光学部材用粘着剤組成物からなる粘着剤層は、初期のぬれ性が低下して、被着体に対する密着性が低下し、信頼性に劣る。
上記混合モノマーにおける2-ヒドロキシエチルアクリレート又はN-ビニルピロリドンの割合は、好ましい下限が5重量%、更に好ましい下限が8重量%であり、好ましい上限が20重量%、更に好ましい上限が15重量%である。
上記混合モノマーにおける上記一般式(1-1)で表される構造を有するモノマー、又は、上記一般式(1-2)で表される構造を有するモノマーの割合は、好ましい下限が1重量%、より好ましい下限が2重量%、好ましい上限が20重量%、より好ましい上限が15重量%である。
When the ratio of the monomer having the hydrophilic group in the mixed monomer is too small, the obtained pressure-sensitive adhesive composition for optical members cannot sufficiently suppress whitening that occurs under high temperature and high humidity. When the ratio of the monomer having the hydrophilic group in the mixed monomer is too large, the pressure-sensitive adhesive layer made of the obtained pressure-sensitive adhesive composition for optical members has reduced initial wettability, and adhesion to an adherend. Lower and less reliable.
The proportion of 2-hydroxyethyl acrylate or N-vinylpyrrolidone in the mixed monomer is preferably 5% by weight, more preferably 8% by weight, more preferably 20% by weight, and still more preferably 15% by weight. is there.
The proportion of the monomer having the structure represented by the general formula (1-1) in the mixed monomer or the monomer having the structure represented by the general formula (1-2) is preferably 1% by weight as a lower limit. A more preferred lower limit is 2% by weight, a preferred upper limit is 20% by weight, and a more preferred upper limit is 15% by weight.
上記混合モノマーは、ビシクロ環構造と1つのオレフィン性二重結合とを有するモノマー10~60重量%を含有することが好ましい。
上記混合モノマーが上記ビシクロ環構造と1つのオレフィン性二重結合とを有するモノマーを含有することで、得られる光学部材用粘着剤組成物は、被着体に対する粘着力が劇的に向上する。このような粘着力の向上は、被着体がポリカーボネート板又はアクリル板である場合に特に優れた効果を発揮する。
The mixed monomer preferably contains 10 to 60% by weight of a monomer having a bicyclo ring structure and one olefinic double bond.
When the mixed monomer contains a monomer having the bicyclo ring structure and one olefinic double bond, the pressure-sensitive adhesive composition for an optical member obtained has dramatically improved adhesive strength to an adherend. Such an improvement in adhesive strength exhibits a particularly excellent effect when the adherend is a polycarbonate plate or an acrylic plate.
ポリカーボネート板及びアクリル板は水分を吸収しやすく、高温条件下では水分が気化して、アウトガスが生じることが知られている。そのため、被着体がポリカーボネート板又はアクリル板である場合、高温条件下では、アウトガスのガス圧によって気泡が成長し、ポリカーボネート板又はアクリル板と粘着剤層との界面には浮き剥がれが生じやすい。
上記混合モノマーが上記ビシクロ環構造と1つのオレフィン性二重結合とを有するモノマーを含有することで、得られる光学部材用粘着剤組成物は、被着体に対する粘着力が劇的に向上し、被着体がポリカーボネート板又はアクリル板である場合にも被着体と粘着剤層との界面に発生する浮き剥がれを抑制することができる。
なお、ポリカーボネート板及びアクリル板は、例えば、携帯電話、携帯情報端末等の入力装置のタッチパネル等に用いられている。
It is known that the polycarbonate plate and the acrylic plate easily absorb moisture, and the moisture is vaporized under high temperature conditions to generate outgas. Therefore, when the adherend is a polycarbonate plate or an acrylic plate, bubbles grow due to the gas pressure of the outgas under high temperature conditions, and the interface between the polycarbonate plate or the acrylic plate and the pressure-sensitive adhesive layer tends to float off.
When the mixed monomer contains a monomer having the bicyclo ring structure and one olefinic double bond, the resulting pressure-sensitive adhesive composition for an optical member has dramatically improved adhesion to an adherend, Even when the adherend is a polycarbonate plate or an acrylic plate, it is possible to suppress the floating peeling that occurs at the interface between the adherend and the pressure-sensitive adhesive layer.
The polycarbonate plate and the acrylic plate are used for, for example, a touch panel of an input device such as a mobile phone or a portable information terminal.
上記ビシクロ環構造は特に限定されず、上記ビシクロ環構造を有する官能基として、例えば、ビシクロ[1.1.0]ブチル基、ビシクロ[1.1.1]ペンチル基、ビシクロ[2.1.0]ペンチル基、ビシクロ[3.1.0]ヘキシル基、ビシクロ[2.1.1]ヘキシル基、ビシクロ[2.2.0]ヘキシル基、ビシクロ[2.2.1]ヘプチル基、ビシクロ[3.1.1]ヘプチル基、ビシクロ[3.2.0]ヘプチル基、ビシクロ[4.1.0]ヘプチル基、ビシクロ[2.2.2]オクチル基、ビシクロ[3.2.1]オクチル基、ビシクロ[3.3.0]オクチル基、ビシクロ[4.1.1]オクチル基、ビシクロ[4.2.0]オクチル基、ビシクロ[5.1.0]オクチル基、ビシクロ[3.2.2]ノニル基、ビシクロ[3.3.1]ノニル基、ビシクロ[4.2.1]ノニル基、ビシクロ[4.3.0]ノニル基、ビシクロ[5.1.1]ノニル基、ビシクロ[5.2.0]ノニル基、ビシクロ[6.1.0]ノニル基、ビシクロ[4.3.1]デシル基、及び、これらの水素原子の一部を鎖状アルキル基又は環状アルキル基で置換した構造を有する官能基等が挙げられる。なお、上記置換は1箇所であってもよく、複数箇所であってもよい。なかでも、上記ビシクロ環構造を有する官能基として、ノルボルニル基、イソボルニル基が好ましく、イソボルニル基が特に好ましい。 The bicyclo ring structure is not particularly limited, and examples of the functional group having the bicyclo ring structure include a bicyclo [1.1.0] butyl group, a bicyclo [1.1.1] pentyl group, and a bicyclo [2.1. 0] pentyl group, bicyclo [3.1.0] hexyl group, bicyclo [2.1.1] hexyl group, bicyclo [2.2.0] hexyl group, bicyclo [2.2.1] heptyl group, bicyclo [3.1.1] heptyl group, bicyclo [3.2.0] heptyl group, bicyclo [4.1.0] heptyl group, bicyclo [2.2.2] octyl group, bicyclo [3.2.1] ] Octyl group, bicyclo [3.3.0] octyl group, bicyclo [4.1.1] octyl group, bicyclo [4.2.0] octyl group, bicyclo [5.1.0] octyl group, bicyclo [ 3.2.2] Nonyl group, bicyclo 3.3.1] Nonyl group, bicyclo [4.2.1] nonyl group, bicyclo [4.3.0] nonyl group, bicyclo [5.1.1] nonyl group, bicyclo [5.2.0] Nonyl group, bicyclo [6.1.0] nonyl group, bicyclo [4.3.1] decyl group, and a functional group having a structure in which a part of these hydrogen atoms is substituted with a chain alkyl group or a cyclic alkyl group Groups and the like. In addition, the said substitution may be one place and may be multiple places. Especially, as a functional group which has the said bicyclo ring structure, a norbornyl group and an isobornyl group are preferable and an isobornyl group is especially preferable.
上記オレフィン性二重結合は特に限定されず、上記オレフィン性二重結合を有する官能基として、例えば、(メタ)アクリロイル基、ビニル基、アリル基等が挙げられる。なかでも、上記オレフィン性二重結合を有する官能基として、(メタ)アクリロイル基が好ましい。 The olefinic double bond is not particularly limited, and examples of the functional group having the olefinic double bond include a (meth) acryloyl group, a vinyl group, and an allyl group. Of these, a (meth) acryloyl group is preferred as the functional group having the olefinic double bond.
上記ビシクロ環構造と1つのオレフィン性二重結合とを有するモノマーとして、具体的には、例えば、イソボルニル基と(メタ)アクリロイル基とを有するイソボルニル(メタ)アクリレートが好ましい。 Specifically, as the monomer having the bicyclo ring structure and one olefinic double bond, for example, isobornyl (meth) acrylate having an isobornyl group and a (meth) acryloyl group is preferable.
上記混合モノマーにおける上記ビシクロ環構造と1つのオレフィン性二重結合とを有するモノマーの割合が10重量%未満であると、得られる光学部材用粘着剤組成物は、被着体に対する粘着力が低下して、信頼性が低下することがある。上記混合モノマーにおける上記ビシクロ環構造と1つのオレフィン性二重結合とを有するモノマーの割合が60重量%を超えると、得られるアクリル共重合体のガラス転移温度が上がることがある。このようなアクリル共重合体を含有する光学部材用粘着剤組成物からなる粘着剤層は、被着体に対する密着性が低下して、信頼性が低下することがある。
上記混合モノマーにおける上記ビシクロ環構造と1つのオレフィン性二重結合とを有するモノマーの割合は、より好ましい下限が15重量%、更に好ましい下限が25重量%、より好ましい上限が55重量%、更に好ましい上限が40重量%である。
When the proportion of the monomer having the bicyclo ring structure and one olefinic double bond in the mixed monomer is less than 10% by weight, the resulting pressure-sensitive adhesive composition for optical members has a reduced adhesive force to the adherend. As a result, reliability may be reduced. When the ratio of the monomer having the bicyclo ring structure and one olefinic double bond in the mixed monomer exceeds 60% by weight, the glass transition temperature of the resulting acrylic copolymer may increase. In the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical members containing such an acrylic copolymer, the adhesiveness to the adherend is lowered, and the reliability may be lowered.
The ratio of the monomer having the bicyclo ring structure and one olefinic double bond in the mixed monomer is more preferably a lower limit of 15% by weight, a still more preferable lower limit of 25% by weight, and a more preferable upper limit of 55% by weight, still more preferable. The upper limit is 40% by weight.
上記混合モノマーは、下記一般式(2)で表される構造を有する(メタ)アクリル酸エステルモノマー30~80重量%を含有することが好ましい。本明細書中、下記一般式(2)で表される構造を有する(メタ)アクリル酸エステルモノマーを、単に「(メタ)アクリル酸エステルモノマー」ともいう。 The mixed monomer preferably contains 30 to 80% by weight of a (meth) acrylic acid ester monomer having a structure represented by the following general formula (2). In this specification, the (meth) acrylic acid ester monomer having a structure represented by the following general formula (2) is also simply referred to as “(meth) acrylic acid ester monomer”.
一般式(2)中、Rは水素原子又はメチル基を表し、Rは炭素数3~14のアルキル基を表す。Rのアルキル基の水素原子は、シクロアルキル基に置換されていてもよい。 In the general formula (2), R 5 represents a hydrogen atom or a methyl group, and R 6 represents an alkyl group having 3 to 14 carbon atoms. The hydrogen atom of the alkyl group of R 6 may be substituted with a cycloalkyl group.
上記Rのアルキル基の炭素数が2以下又は15以上であると、得られるアクリル共重合体のガラス転移温度が上がることがある。このようなアクリル共重合体を含有する光学部材用粘着剤組成物からなる粘着剤層は、被着体に対する密着性が低下して、信頼性が低下することがある。上記Rのアルキル基の炭素数は4~12であることが好ましい。
また、上記Rのアルキル基の水素原子は、シクロアルキル基に置換されていてもよい。上記シクロアルキル基は特に限定されず、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等が挙げられる。
When the carbon number of the alkyl group of R 6 is 2 or less or 15 or more, the glass transition temperature of the resulting acrylic copolymer may be increased. The pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for an optical member containing such an acrylic copolymer may deteriorate in reliability due to a decrease in adhesion to an adherend. The alkyl group of R 6 preferably has 4 to 12 carbon atoms.
Moreover, the hydrogen atom of the alkyl group of R 6 may be substituted with a cycloalkyl group. The cycloalkyl group is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
上記(メタ)アクリル酸エステルモノマーは特に限定されず、例えば、ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、プロピル(メタ)アクリレート、2-エチルオクチル(メタ)アクリレート、ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、イソテトラデシル(メタ)アクリレート等が挙げられる。
上記混合モノマーがこのようなモノマーを含有することで、得られる光学部材用粘着剤組成物からなる粘着剤層は、凝集力、初期接着性、密着性等が向上する。なかでも、低温弾性率が低く、初期のぬれ性が高い粘着剤層が得られることから、上記(メタ)アクリル酸エステルモノマーは、2-エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート及びブチル(メタ)アクリレートからなる群より選択される少なくとも1つの(メタ)アクリル酸エステルモノマーを含有することが好ましい。
The (meth) acrylic acid ester monomer is not particularly limited. For example, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, propyl (meth) acrylate, 2-ethyloctyl (meth) acrylate Nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isotetradecyl (meth) acrylate, and the like.
When the mixed monomer contains such a monomer, the pressure-sensitive adhesive layer made of the obtained pressure-sensitive adhesive composition for optical members is improved in cohesive force, initial adhesiveness, adhesion and the like. Among these, since a pressure-sensitive adhesive layer having a low low-temperature elastic modulus and high initial wettability is obtained, the (meth) acrylic acid ester monomer includes 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate and butyl ( It is preferable to contain at least one (meth) acrylic acid ester monomer selected from the group consisting of (meth) acrylates.
上記混合モノマーにおける上記(メタ)アクリル酸エステルモノマーの割合が30重量%未満であると、得られる光学部材用粘着剤組成物からなる粘着剤層は、低温弾性率が高くなって初期のぬれ性が低下し、被着体に対する密着性が低下して、信頼性が低下することがある。上記混合モノマーにおける上記(メタ)アクリル酸エステルモノマーの割合が80重量%を超えると、得られる光学部材用粘着剤組成物からなる粘着剤層は、凝集力が低下して加工性が低下することがある。
上記混合モノマーにおける上記(メタ)アクリル酸エステルモノマーの割合は、より好ましい下限が40重量%、より好ましい上限が65重量%である。
When the proportion of the (meth) acrylic acid ester monomer in the mixed monomer is less than 30% by weight, the resulting pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical members has a high low-temperature elastic modulus and initial wettability. May decrease, adhesion to an adherend may decrease, and reliability may decrease. When the proportion of the (meth) acrylic acid ester monomer in the mixed monomer exceeds 80% by weight, the pressure-sensitive adhesive layer made of the resulting pressure-sensitive adhesive composition for optical members has reduced cohesive force and processability. There is.
As for the ratio of the (meth) acrylic acid ester monomer in the mixed monomer, a more preferable lower limit is 40% by weight, and a more preferable upper limit is 65% by weight.
上記混合モノマーは、カルボキシル基と1つのオレフィン性二重結合とを有するモノマーを含有していてもよい。
上記混合モノマーが上記カルボキシル基と1つのオレフィン性二重結合とを有するモノマーを含有することで、得られるアクリル共重合体は分子間相互作用が増大する。このようなアクリル共重合体を含有する光学部材用粘着剤組成物からなる粘着剤層は、凝集力が向上する。
なお、上記混合モノマーは、上記カルボキシル基と1つのオレフィン性二重結合とを有するモノマーを含有していなくてもよい。
The mixed monomer may contain a monomer having a carboxyl group and one olefinic double bond.
When the mixed monomer contains a monomer having the carboxyl group and one olefinic double bond, the resulting acrylic copolymer has an increased intermolecular interaction. The pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical members containing such an acrylic copolymer has improved cohesive strength.
In addition, the said mixed monomer does not need to contain the monomer which has the said carboxyl group and one olefinic double bond.
上記カルボキシル基と1つのオレフィン性二重結合とを有するモノマーは特に限定されず、例えば、(メタ)アクリル酸、(メタ)アクリロイル酢酸、(メタ)アクリロイルプロピオン酸、(メタ)アクリロイル酪酸、(メタ)アクリロイルペンタン酸、クロトン酸等の不飽和モノカルボン酸、マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸等の不飽和ジカルボン酸等が挙げられる。 The monomer which has the said carboxyl group and one olefinic double bond is not specifically limited, For example, (meth) acrylic acid, (meth) acryloyl acetic acid, (meth) acryloyl propionic acid, (meth) acryloyl butyric acid, (meth ) Unsaturated monocarboxylic acids such as acryloylpentanoic acid and crotonic acid, and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid.
上記混合モノマーにおける上記カルボキシル基と1つのオレフィン性二重結合とを有するモノマーの割合は特に限定されないが、2重量%以下であることが好ましい。上記カルボキシル基と1つのオレフィン性二重結合とを有するモノマーの割合が2重量%を超えると、得られる光学部材用粘着剤組成物は、ITO等の金属又は金属酸化物を含有する金属薄膜を被着体とする場合に、該金属薄膜を劣化させやすくなることがある。
上記混合モノマーにおける上記カルボキシル基と1つのオレフィン性二重結合とを有するモノマーの割合は、1重量%以下であることがより好ましく、0.5重量%以下であることが更に好ましい。
The ratio of the monomer having the carboxyl group and one olefinic double bond in the mixed monomer is not particularly limited, but is preferably 2% by weight or less. When the ratio of the monomer having the carboxyl group and one olefinic double bond exceeds 2% by weight, the resulting pressure-sensitive adhesive composition for an optical member is obtained from a metal thin film containing a metal such as ITO or a metal oxide. In the case of an adherend, the metal thin film may be easily deteriorated.
The ratio of the monomer having the carboxyl group and one olefinic double bond in the mixed monomer is more preferably 1% by weight or less, and further preferably 0.5% by weight or less.
上記アクリル共重合体を製造する方法は特に限定されず、例えば、上記親水性基を有するモノマー、及び、必要に応じて配合される上記ビシクロ環構造と1つのオレフィン性二重結合とを有するモノマー等の他のモノマーを含有する混合モノマーを、重合開始剤の存在下にてラジカル重合させる方法等が挙げられる。 The method for producing the acrylic copolymer is not particularly limited. For example, the monomer having the hydrophilic group and the monomer having the bicyclo ring structure and one olefinic double bond to be blended as necessary. And a method of radical polymerization of a mixed monomer containing other monomers in the presence of a polymerization initiator.
上記重合方法は特に限定されず、例えば、溶液重合、乳化重合、懸濁重合、塊状重合等の従来公知の重合方法が挙げられる。
上記溶液重合に用いる溶媒は特に限定されず、例えば、酢酸エチル、トルエン、ジメチルスルホキシド、エタノール、アセトン、ジエチルエーテル等が挙げられる。
The said polymerization method is not specifically limited, For example, conventionally well-known polymerization methods, such as solution polymerization, emulsion polymerization, suspension polymerization, block polymerization, are mentioned.
The solvent used for the solution polymerization is not particularly limited, and examples thereof include ethyl acetate, toluene, dimethyl sulfoxide, ethanol, acetone, diethyl ether and the like.
上記溶液重合に用いる溶媒の配合量は特に限定されないが、上記混合モノマー100重量部に対する好ましい下限が25重量部、好ましい上限が300重量部である。上記溶媒の配合量が25重量部未満であると、得られるアクリル共重合体の分子量分布が広くなることがある。このようなアクリル共重合体を含有する光学部材用粘着剤組成物からなる粘着剤層は、被着体に対する粘着力及び凝集力が低下して、信頼性が低下することがある。上記溶媒の配合量が300重量部を超えると、得られるアクリル共重合体を用いて光学部材用粘着剤組成物を調製し、粘着剤層を形成する際に、溶媒を除去する手間が必要となることがある。 Although the compounding quantity of the solvent used for the said solution polymerization is not specifically limited, The preferable minimum with respect to 100 weight part of said mixed monomers is 25 weight part, and a preferable upper limit is 300 weight part. When the blending amount of the solvent is less than 25 parts by weight, the molecular weight distribution of the resulting acrylic copolymer may be broadened. The pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for an optical member containing such an acrylic copolymer may reduce the adhesive force and cohesive force with respect to the adherend, thereby reducing the reliability. When the amount of the solvent exceeds 300 parts by weight, it is necessary to remove the solvent when preparing the pressure-sensitive adhesive composition for an optical member using the resulting acrylic copolymer and forming the pressure-sensitive adhesive layer. May be.
上記重合開始剤は特に限定されず、例えば、過硫酸塩、有機過酸化物、アゾ化合物等が挙げられる。なかでも、ITO等の金属又は金属酸化物を含有する金属薄膜を被着体とする場合に該金属薄膜に与える影響を考慮すると、アゾ化合物が好ましい。
上記過硫酸塩は特に限定されず、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等が挙げられる。上記有機過酸化物は特に限定されず、例えば、1,1-ビス(t-ヘキシルパーオキシ)-3,3,5-トリメチルシクロヘキサン、t-ヘキシルパーオキシピバレート、t-ブチルパーオキシピバレート、ラウロイルパーオキシド、2,5-ジメチル-2,5-ビス(2-エチルヘキサノイルパーオキシ)ヘキサン、t-ヘキシルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシイソブチレート、t-ブチルパーオキシ-3,5,5-トリメチルヘキサノエート、t-ブチルパーオキシラウレート等が挙げられる。上記アゾ化合物は特に限定されず、例えば、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、4,4’-アゾビス(4-シアノペンタン酸)、2,2’-アゾビス(2-メチルブチロニトリル)、アゾビスシクロヘキサンカルボニトリル等が挙げられる。
これらの重合開始剤は単独で用いてもよいし、2種以上を併用してもよい。
The said polymerization initiator is not specifically limited, For example, a persulfate, an organic peroxide, an azo compound etc. are mentioned. Among these, an azo compound is preferable in consideration of the influence on the metal thin film when a metal thin film containing a metal such as ITO or a metal oxide is used as an adherend.
The persulfate is not particularly limited, and examples thereof include potassium persulfate, sodium persulfate, and ammonium persulfate. The organic peroxide is not particularly limited. For example, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, t-hexylperoxypivalate, t-butylperoxypivalate , Lauroyl peroxide, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexa Noate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate and the like. The azo compound is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanopentane) Acid), 2,2′-azobis (2-methylbutyronitrile), azobiscyclohexanecarbonitrile and the like.
These polymerization initiators may be used alone or in combination of two or more.
上記重合開始剤の配合量は特に限定されないが、上記混合モノマー100重量部に対する好ましい下限が0.02重量部、好ましい上限が0.5重量部である。上記重合開始剤の配合量が0.02重量部未満であると、重合反応が不充分となったり、重合反応に長時間を要したりすることがある。上記重合開始剤の配合量が0.5重量部を超えると、得られるアクリル共重合体の重量平均分子量が低くなりすぎたり、分子量分布が広くなりすぎたりすることがある。このようなアクリル共重合体を含有する光学部材用粘着剤組成物からなる粘着剤層は、被着体に対する粘着力及び凝集力が低下して、信頼性が低下することがある。 Although the compounding quantity of the said polymerization initiator is not specifically limited, The preferable minimum with respect to 100 weight part of said mixed monomers is 0.02 weight part, and a preferable upper limit is 0.5 weight part. When the blending amount of the polymerization initiator is less than 0.02 parts by weight, the polymerization reaction may be insufficient, or the polymerization reaction may take a long time. When the blending amount of the polymerization initiator exceeds 0.5 parts by weight, the weight average molecular weight of the resulting acrylic copolymer may become too low or the molecular weight distribution may become too wide. The pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for an optical member containing such an acrylic copolymer may reduce the adhesive force and cohesive force with respect to the adherend, thereby reducing the reliability.
上記アクリル共重合体の重量平均分子量は、好ましい下限が20万、好ましい上限が150万である。上記アクリル共重合体の重量平均分子量が20万未満であると、得られる光学部材用粘着剤組成物からなる粘着剤層は、高温弾性率が低下して、信頼性が低下することがある。上記アクリル共重合体の重量平均分子量が150万を超えると、アクリル共重合体の流動性が低下することがある。このようなアクリル共重合体を含有する光学部材用粘着剤組成物からなる粘着剤層は、被着体に対する密着性が低下して、信頼性が低下することがある。
上記アクリル共重合体の重量平均分子量のより好ましい下限は30万、更に好ましい下限は40万、更により好ましい下限は50万であり、より好ましい上限は120万、更に好ましい上限は90万、更により好ましい上限は65万である。
As for the weight average molecular weight of the acrylic copolymer, a preferable lower limit is 200,000 and a preferable upper limit is 1,500,000. When the weight average molecular weight of the acrylic copolymer is less than 200,000, the pressure-sensitive adhesive layer made of the obtained pressure-sensitive adhesive composition for optical members may have a reduced high-temperature elastic modulus and a reduced reliability. When the weight average molecular weight of the acrylic copolymer exceeds 1,500,000, the fluidity of the acrylic copolymer may be lowered. In the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical members containing such an acrylic copolymer, the adhesiveness to the adherend is lowered, and the reliability may be lowered.
The more preferable lower limit of the weight average molecular weight of the acrylic copolymer is 300,000, the still more preferable lower limit is 400,000, the still more preferable lower limit is 500,000, the more preferable upper limit is 1,200,000, and the still more preferable upper limit is 900,000. A preferable upper limit is 650,000.
なお、本明細書において重量平均分子量とは、ゲルパーミエーションクロマトグラフィー(GPC)法により測定しポリスチレン換算により求めた値を意味する。具体的には、例えば、上記アクリル共重合体をテトラヒドロフラン(THF)により100倍に希釈して得られた希釈液をフィルターで濾過し、得られた濾液をカラム(例えば、Waters社製の商品名「2690 Separations Model」等)を用いてGPC法により測定しポリスチレン換算によって重量平均分子量を求めることができる。 In addition, in this specification, a weight average molecular weight means the value measured by gel permeation chromatography (GPC) method and calculated | required by polystyrene conversion. Specifically, for example, the diluted solution obtained by diluting the acrylic copolymer 100 times with tetrahydrofuran (THF) is filtered through a filter, and the obtained filtrate is filtered with a column (for example, a product name manufactured by Waters). The weight average molecular weight can be determined by polystyrene conversion using a “2690 Separations Model” or the like.
上記アクリル共重合体を含有する溶液は、低粘度の溶液となる。そのため、該アクリル共重合体を含有する光学部材用粘着剤組成物を用いて粘着剤層を形成する際には、塗工のために必要とされる溶剤の量が少なく、取扱性に優れる。また、厚い粘着剤層を作製しやすく、粘着剤層の被着体に対する粘着力を高めることができる。
上記アクリル共重合体を含有する光学部材用粘着剤組成物溶液の粘度は特に限定されないが、B型粘度計(「B8U型粘度計」、東京計器社製)を用いて温度25℃の条件で測定した粘度の好ましい下限が500mPa・s、好ましい上限が100000mPa・sである。
The solution containing the acrylic copolymer is a low viscosity solution. Therefore, when forming the pressure-sensitive adhesive layer using the pressure-sensitive adhesive composition for optical members containing the acrylic copolymer, the amount of the solvent required for coating is small, and the handleability is excellent. Moreover, it is easy to produce a thick adhesive layer, and the adhesive force of the adhesive layer to the adherend can be increased.
The viscosity of the pressure-sensitive adhesive composition solution for an optical member containing the acrylic copolymer is not particularly limited, but a B-type viscometer (“B8U-type viscometer”, manufactured by Tokyo Keiki Co., Ltd.) is used at a temperature of 25 ° C. The preferable lower limit of the measured viscosity is 500 mPa · s, and the preferable upper limit is 100,000 mPa · s.
本発明の光学部材用粘着剤組成物は、上記アクリル共重合体のほかに、架橋剤を含有してもよい。
上記架橋剤を含有することで、上記アクリル共重合体に架橋構造を形成することができる。また、上記架橋剤の種類又は量を適宜調整することで、得られる光学部材用粘着剤組成物からなる粘着剤層のゲル分率を調整することができる。
The pressure-sensitive adhesive composition for an optical member of the present invention may contain a crosslinking agent in addition to the acrylic copolymer.
By containing the crosslinking agent, a crosslinked structure can be formed in the acrylic copolymer. Moreover, the gel fraction of the adhesive layer which consists of an adhesive composition for optical members obtained by adjusting the kind or quantity of the said crosslinking agent suitably can be adjusted.
上記架橋剤は特に限定されず、例えば、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、金属キレート型架橋剤等が挙げられる。なかでも、耐熱性及び耐久性等の性能を発現しやすいことから、本発明の光学部材用粘着剤組成物は、イソシアネート系架橋剤及びエポキシ系架橋剤からなる群より選択される少なくとも1つの架橋剤を含有することが好ましい。 The said crosslinking agent is not specifically limited, For example, an isocyanate type crosslinking agent, an aziridine type crosslinking agent, an epoxy-type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned. Especially, since it is easy to express performance, such as heat resistance and durability, the adhesive composition for optical members of this invention is at least 1 bridge | crosslinking selected from the group which consists of an isocyanate type crosslinking agent and an epoxy type crosslinking agent. It is preferable to contain an agent.
上記イソシアネート系架橋剤は特に限定されないが、脂肪族イソシアネート系架橋剤が好ましい。上記脂肪族イソシアネート系架橋剤のうち、市販品として、例えば、コロネートHX(日本ポリウレタン社製)等が挙げられる。
上記エポキシ系架橋剤は特に限定されないが、脂肪族エポキシ系架橋剤が好ましい。上記脂肪族エポキシ系架橋剤のうち、市販品として、例えば、デナコールEX212、デナコールEX214(いずれもナガセケムテックス社製)等が挙げられる。
Although the said isocyanate type crosslinking agent is not specifically limited, An aliphatic isocyanate type crosslinking agent is preferable. Among the aliphatic isocyanate-based crosslinking agents, examples of commercially available products include Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.).
Although the said epoxy-type crosslinking agent is not specifically limited, An aliphatic epoxy-type crosslinking agent is preferable. Among the above-mentioned aliphatic epoxy crosslinking agents, examples of commercially available products include Denacol EX212 and Denacol EX214 (both manufactured by Nagase ChemteX Corporation).
上記架橋剤の配合量は特に限定されないが、上記アクリル共重合体100重量部に対する好ましい下限が0.1重量部、好ましい上限が10重量部である。上記架橋剤の配合量が0.1重量部未満であると、上記アクリル共重合体の架橋が不充分となり、得られる光学部材用粘着剤組成物からなる粘着剤層は、凝集力が低下して加工性が低下することがある。上記架橋剤の配合量が10重量部を超えると、得られる光学部材用粘着剤組成物からなる粘着剤層は、被着体に対する粘着力及び初期接着性が低下して、信頼性が低下することがある。
上記架橋剤の配合量は、上記アクリル共重合体100重量部に対するより好ましい下限が0.3重量部、より好ましい上限が3.0重量部である。
Although the compounding quantity of the said crosslinking agent is not specifically limited, The preferable minimum with respect to 100 weight part of said acrylic copolymers is 0.1 weight part, and a preferable upper limit is 10 weight part. When the blending amount of the crosslinking agent is less than 0.1 parts by weight, the acrylic copolymer is insufficiently crosslinked, and the pressure-sensitive adhesive layer made of the resulting pressure-sensitive adhesive composition for optical members has reduced cohesive force. As a result, workability may be reduced. When the blending amount of the crosslinking agent exceeds 10 parts by weight, the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical members is deteriorated in the adhesive strength and initial adhesiveness to the adherend, and the reliability is lowered. Sometimes.
As for the compounding quantity of the said crosslinking agent, the more preferable minimum with respect to 100 weight part of said acrylic copolymers is 0.3 weight part, and a more preferable upper limit is 3.0 weight part.
本発明の光学部材用粘着剤組成物は、更に、粘着付与樹脂を含有してもよい。
上記粘着付与樹脂は特に限定されず、例えば、キシレン樹脂、フェノール樹脂、ロジン系樹脂、テルペン系樹脂等が挙げられる。これらの粘着付与樹脂は、単独で用いてもよいし、2種以上を併用してもよい。なかでも、キシレン樹脂が好ましく、キシレン樹脂のアルキルフェノール反応物がより好ましい。
また、上記粘着付与樹脂として、水素添加された樹脂が好ましく、このような水素添加された樹脂を用いることで、得られる光学部材用粘着剤組成物は、透明性が高まる。
The pressure-sensitive adhesive composition for optical members of the present invention may further contain a tackifier resin.
The tackifying resin is not particularly limited, and examples thereof include a xylene resin, a phenol resin, a rosin resin, and a terpene resin. These tackifier resins may be used alone or in combination of two or more. Of these, a xylene resin is preferable, and an alkylphenol reaction product of the xylene resin is more preferable.
Moreover, as the tackifying resin, a hydrogenated resin is preferable. By using such a hydrogenated resin, the pressure-sensitive adhesive composition for an optical member obtained has increased transparency.
本発明の光学部材用粘着剤組成物は、更に、シランカップリング剤を含有してもよい。
上記シランカップリング剤を含有することで、得られる光学部材用粘着剤組成物からなる粘着剤層は、被着体に対する密着性が向上する。
上記シランカップリング剤は特に限定されず、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、メタクリロキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルメチルジメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルトリメチルメトキシシラン、N-(2-アミノエチル)3-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)3-アミノプロピルメチルジメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、γ-メルカプトプロピルトリエトキシシラン、メルカプトブチルトリメトキシシラン、γ-メルカプトプロピルメチルジメトキシシラン等が挙げられる。
The pressure-sensitive adhesive composition for optical members of the present invention may further contain a silane coupling agent.
By containing the said silane coupling agent, the adhesive layer which consists of an adhesive composition for optical members obtained improves the adhesiveness with respect to a to-be-adhered body.
The silane coupling agent is not particularly limited. For example, vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane , Γ-aminopropyltrimethylmethoxysilane, N- (2-aminoethyl) 3-aminopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, γ-mercaptopropyltri Examples include methoxysilane, γ-mercaptopropyltriethoxysilane, mercaptobutyltrimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane.
本発明の光学部材用粘着剤組成物は、更に、本発明の効果を阻害しない範囲内で、必要に応じて従来公知の添加剤を含有してもよい。
上記添加剤は特に限定されず、例えば、充てん剤、老化防止剤等が挙げられる。
The pressure-sensitive adhesive composition for an optical member of the present invention may further contain a conventionally known additive as necessary within the range not impairing the effects of the present invention.
The said additive is not specifically limited, For example, a filler, anti-aging agent, etc. are mentioned.
本発明の光学部材用粘着剤組成物を製造する方法は特に限定されず、例えば、上記アクリル共重合体、及び、必要に応じて、上記架橋剤、上記粘着付与樹脂、上記シランカップリング剤、上記添加剤を混合し、攪拌する方法が挙げられる。 The method for producing the pressure-sensitive adhesive composition for optical members of the present invention is not particularly limited. For example, the acrylic copolymer, and, if necessary, the crosslinking agent, the tackifying resin, the silane coupling agent, The method of mixing and stirring the said additive is mentioned.
本発明の光学部材用粘着剤組成物の用途は特に限定されず、種々の光学部材に対して適用することができる。なかでも、本発明の光学部材用粘着剤組成物を、携帯電話、携帯情報端末等の画像表示装置を製造する際に、画像表示装置の表面を保護するための保護板と、ディスプレイパネルとを貼り合わせるために用いたり、また、携帯電話、携帯情報端末等の入力装置を製造する際に、タッチパネルのポリカーボネート板又はアクリル板と、ディスプレイパネルとを貼り合わせるために用いたりすることが好ましい。
本発明の光学部材用粘着剤組成物は、高温高湿下で生じる白化を抑制することができることから、例えばディスプレイパネルへの貼り合わせ等の高い透明性が要求される光学用途にも好適に適用することができ、高信頼性を実現することができる。
The application of the pressure-sensitive adhesive composition for optical members of the present invention is not particularly limited, and can be applied to various optical members. Among them, the protective composition for protecting the surface of the image display device and the display panel when the image-forming device for an optical member of the present invention is produced using the pressure-sensitive adhesive composition for an optical member of the present invention. It is preferably used for bonding, or used for bonding a polycarbonate plate or an acrylic plate of a touch panel and a display panel when manufacturing an input device such as a mobile phone or a portable information terminal.
Since the pressure-sensitive adhesive composition for optical members of the present invention can suppress whitening that occurs under high temperature and high humidity, it can be suitably applied to optical applications that require high transparency such as bonding to display panels. And high reliability can be realized.
また、本発明の光学部材用粘着剤組成物からなる粘着剤層を有する光学部材用粘着テープを製造し、得られた光学部材用粘着テープを上述の用途に適用してもよい。
本発明の光学部材用粘着剤組成物からなる粘着剤層を有する光学部材用粘着テープもまた、本発明の1つである。
Moreover, you may manufacture the adhesive tape for optical members which has an adhesive layer which consists of an adhesive composition for optical members of this invention, and may apply the obtained adhesive tape for optical members to the above-mentioned use.
The adhesive tape for optical members which has an adhesive layer which consists of an adhesive composition for optical members of this invention is also one of this invention.
上記粘着剤層のゲル分率は特に限定されず、光学部材用粘着テープの用途に合わせて適宜調整することができるが、好ましい下限は30重量%、好ましい上限は95重量%である。上記粘着剤層のゲル分率が30重量%未満であると、光学部材用粘着テープの加工性が低下することがある。上記粘着剤層のゲル分率が95重量%を超えると、粘着剤層は初期のぬれ性が低下し、被着体に対する密着性が低下して、信頼性が低下することがある。
上記粘着剤層のゲル分率のより好ましい下限は40重量%、より好ましい上限は90重量%である。
Although the gel fraction of the said adhesive layer is not specifically limited, Although it can adjust suitably according to the use of the adhesive tape for optical members, a preferable minimum is 30 weight% and a preferable upper limit is 95 weight%. When the gel fraction of the pressure-sensitive adhesive layer is less than 30% by weight, the processability of the pressure-sensitive adhesive tape for optical members may be lowered. When the gel fraction of the pressure-sensitive adhesive layer exceeds 95% by weight, the initial wettability of the pressure-sensitive adhesive layer is lowered, the adhesion to the adherend is lowered, and the reliability may be lowered.
The minimum with a more preferable gel fraction of the said adhesive layer is 40 weight%, and a more preferable upper limit is 90 weight%.
なお、上記ゲル分率は、下記の方法により測定することができる。
まず、本発明の光学部材用粘着テープを50mm×25mmの平面長方形状に切断して試験片を作製する。得られた試験片の粘着剤層をスプーンを使ってかきとって粘着剤の塊を作製し、粘着剤の塊を酢酸エチル中に23℃にて24時間浸漬した後、200メッシュのステンレスメッシュを介して粘着剤の塊を酢酸エチルから取り出して、110℃の条件下で1時間乾燥させる。そして、乾燥後の粘着剤の塊の重量を測定し、下記式(1)を用いてゲル分率を算出する。
ゲル分率(重量%)=100×(W)/(W) (1)
式(1)中、Wは浸漬前の粘着剤の塊の乾燥した状態での重量を表し、Wは浸漬し乾燥した後の粘着剤の塊の重量を表す。なお、必要に応じて試験片の粘着剤層をスプーンを使ってかきとる前に、試験片を溶剤に浸して粘着剤層を膨潤させておいてもよい。
The gel fraction can be measured by the following method.
First, the pressure-sensitive adhesive tape for optical members of the present invention is cut into a flat rectangular shape of 50 mm × 25 mm to produce a test piece. The pressure-sensitive adhesive layer of the obtained test piece was scraped with a spoon to prepare a pressure-sensitive adhesive lump. After the pressure-sensitive adhesive lump was immersed in ethyl acetate at 23 ° C. for 24 hours, a 200-mesh stainless mesh was The mass of the pressure-sensitive adhesive is taken out from the ethyl acetate and dried at 110 ° C. for 1 hour. And the weight of the lump of the adhesive after drying is measured, and a gel fraction is computed using following formula (1).
Gel fraction (% by weight) = 100 × (W 2 ) / (W 1 ) (1)
Wherein (1), W 1 represents the weight of the dry conditions of the mass of the pressure-sensitive adhesive before immersion, W 2 represents the weight of the mass of the pressure-sensitive adhesive after immersing and drying. In addition, before scraping off the adhesive layer of a test piece using a spoon as needed, the test piece may be immersed in a solvent to swell the adhesive layer.
上記粘着剤層の厚みは特に限定されないが、好ましい下限が5μm、好ましい上限が1mmである。上記粘着剤層の厚みが5μm未満であると、粘着剤層は、被着体に対する粘着力が低下して、信頼性が低下することがある。上記粘着剤層の厚みが1mmを超えると、粘着剤成分の染み出し等が生じ、取扱性が低下することがある。上記粘着剤層の厚みのより好ましい下限は10μm、更に好ましい下限は20μmであり、より好ましい上限は500μm、更に好ましい上限は300μmである。 Although the thickness of the said adhesive layer is not specifically limited, A preferable minimum is 5 micrometers and a preferable upper limit is 1 mm. When the thickness of the pressure-sensitive adhesive layer is less than 5 μm, the pressure-sensitive adhesive layer may be less reliable due to a decrease in the adhesive force to the adherend. When the thickness of the pressure-sensitive adhesive layer exceeds 1 mm, the pressure-sensitive adhesive component oozes out and the handleability may deteriorate. A more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 10 μm, a further preferable lower limit is 20 μm, a more preferable upper limit is 500 μm, and a further preferable upper limit is 300 μm.
本発明の光学部材用粘着テープは、基材を有さないノンサポートタイプであってもよいし、基材の両面に粘着剤層が形成されたサポートタイプであってもよい。
上記基材は、透明性を有する基材であれば特に限定されず、例えば、アクリル、オレフィン、ポリカーボネート、塩化ビニル、ABS、ポリエチレンテレフタレート(PET)、ナイロン、ウレタン、ポリイミド等の透明な樹脂からなるシート、網目状の構造を有するシート、孔が開けられたシート等が挙げられる。
The pressure-sensitive adhesive tape for optical members of the present invention may be a non-support type that does not have a base material, or may be a support type in which pressure-sensitive adhesive layers are formed on both surfaces of the base material.
The base material is not particularly limited as long as it is a transparent base material. For example, the base material is made of a transparent resin such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), nylon, urethane, and polyimide. Examples thereof include a sheet, a sheet having a network structure, and a sheet having holes.
上記基材の厚みは特に限定されないが、好ましい下限が2μm、好ましい上限が200μmである。上記基材の厚みが2μm未満であると、得られる光学部材用粘着テープの強度が不足し、破れたり、取り扱いが困難になったりすることがある。上記基材の厚みが200μmを超えると、基材の腰が強すぎて、得られる光学部材用粘着テープの段差への追従性が悪くなることがある。上記基材の厚みのより好ましい下限は5μm、より好ましい上限は100μmである。 Although the thickness of the said base material is not specifically limited, A preferable minimum is 2 micrometers and a preferable upper limit is 200 micrometers. When the thickness of the base material is less than 2 μm, the strength of the obtained pressure-sensitive adhesive tape for optical members is insufficient, and it may be torn or difficult to handle. When the thickness of the base material exceeds 200 μm, the base material is too strong, and the followability to the step of the obtained pressure-sensitive adhesive tape for optical members may be deteriorated. A more preferable lower limit of the thickness of the substrate is 5 μm, and a more preferable upper limit is 100 μm.
本発明の光学部材用粘着テープを製造する方法は特に限定されない。ノンサポートタイプの光学部材用粘着テープを製造する方法として、例えば、本発明の光学部材用粘着剤組成物を離型紙又は離型フィルムの離型処理面に塗工することによって粘着剤層を形成し、得られた粘着剤層の上に、離型処理面が粘着剤層に接するようにして新たに用意した離型紙又は離型フィルムを重ね合わせて積層体を得た後、得られた積層体をゴムローラ等により加圧する方法等が挙げられる。 The method for producing the pressure-sensitive adhesive tape for optical members of the present invention is not particularly limited. As a method for producing a non-support type pressure-sensitive adhesive tape for optical members, for example, the pressure-sensitive adhesive layer is formed by coating the pressure-sensitive adhesive composition for optical members of the present invention on the release paper or release film of the release film. Then, on the obtained pressure-sensitive adhesive layer, a newly prepared release paper or release film with a release treatment surface in contact with the pressure-sensitive adhesive layer was overlaid to obtain a laminate, and then the obtained laminate Examples include a method of pressing the body with a rubber roller or the like.
また、本発明の光学部材用粘着テープを製造する方法として、上記親水性基を有するモノマー、及び、必要に応じて配合される上記ビシクロ環構造と1つのオレフィン性二重結合とを有するモノマー等の他のモノマーを含有する混合モノマーを、塊状重合によってラジカル重合させ、上記アクリル共重合体を製造すると同時に一気にテープ化まで行う方法が好適に用いられる。 Moreover, as a method for producing the pressure-sensitive adhesive tape for optical members of the present invention, the monomer having the hydrophilic group, the monomer having the bicyclo ring structure and one olefinic double bond, which are blended as necessary, etc. A method in which a mixed monomer containing other monomers is radically polymerized by bulk polymerization to produce the above acrylic copolymer and at the same time to tape formation at a stretch is suitably used.
上記塊状重合は、重合熱の除去がしやすく、反応制御がしやすいことから、光重合であることが好ましい。
特に、本発明の光学部材用粘着テープを製造する方法として、上記混合モノマー、光重合開始剤、及び、必要に応じて添加剤等を含有し、かつ、溶剤を含有しないモノマー組成物を、一方の面が離型処理された透明な合成樹脂フィルムの離型処理面に塗工してモノマー層を形成した後、このモノマー層上に、一方の面が離型処理された別の透明な合成樹脂フィルムの離型処理面を重ね合わせ、合成樹脂フィルムを透してモノマー層に紫外線照射等の光照射を行うことにより、上記混合モノマーをラジカル重合させる方法が好適に用いられる。
The bulk polymerization is preferably photopolymerization because the heat of polymerization is easily removed and the reaction is easily controlled.
In particular, as a method for producing the pressure-sensitive adhesive tape for optical members of the present invention, a monomer composition containing the above-mentioned mixed monomer, photopolymerization initiator, and, if necessary, an additive and the like and containing no solvent, After forming the monomer layer by coating on the release treatment surface of the transparent synthetic resin film whose surface was release-treated, another transparent composition with one surface being release-treated on this monomer layer A method in which the mixed monomer is radically polymerized by superimposing the release treatment surfaces of the resin film and irradiating the monomer layer with light such as ultraviolet irradiation through the synthetic resin film is preferably used.
また、本発明の光学部材用粘着テープを光重合によって製造する場合には、重合と同時に架橋構造を形成できることから、上記混合モノマーは、重合性官能基を2個以上有する多官能(メタ)アクリレートを含有することが好ましい。
上記多官能(メタ)アクリレートは特に限定されず、例えば、1,6-ヘキサンジオールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、水添ポリブタジエンジ(メタ)アクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ポリウレタンジ(メタ)アクリレート、ポリエステルジ(メタ)アクリレート等が挙げられる。なかでも、得られる粘着剤層の応力分散性の低下が小さく粘着性能に優れる点から、1,6-ヘキサンジオールジアクリレート、ポリプロピレングリコールジアクリレート、水添ポリブタジエンジアクリレート、ポリウレタンジアクリレート、ポリエステルジアクリレートが好ましい。
In addition, when the pressure-sensitive adhesive tape for optical members of the present invention is produced by photopolymerization, a cross-linked structure can be formed simultaneously with the polymerization, so the mixed monomer is a polyfunctional (meth) acrylate having two or more polymerizable functional groups. It is preferable to contain.
The polyfunctional (meth) acrylate is not particularly limited. For example, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, hydrogenated polybutadiene Examples include di (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyurethane di (meth) acrylate, and polyester di (meth) acrylate. Among them, 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, hydrogenated polybutadiene diacrylate, polyurethane diacrylate, and polyester diacrylate are preferred because the pressure dispersion of the resulting pressure-sensitive adhesive layer is small and excellent in adhesive performance. Is preferred.
上記混合モノマーが上記多官能(メタ)アクリレートを含有する場合、上記多官能(メタ)アクリレートの配合量は特に限定されないが、上記混合モノマー中の好ましい下限が0.02重量%、好ましい上限が5重量%である。上記多官能(メタ)アクリレートの配合量が0.02重量%未満であると、上記アクリル共重合体の架橋が不充分となり、得られる粘着剤層は、凝集力が低下して加工性が低下することがある。上記多官能(メタ)アクリレートの配合量が5重量%を超えると、得られる粘着剤層は、被着体に対する粘着力及び初期接着性が低下して、信頼性が低下することがある。
上記多官能(メタ)アクリレートの配合量は、上記混合モノマー中のより好ましい下限が0.05重量%、より好ましい上限が3重量%である。
When the said mixed monomer contains the said polyfunctional (meth) acrylate, the compounding quantity of the said polyfunctional (meth) acrylate is not specifically limited, The preferable minimum in the said mixed monomer is 0.02 weight%, A preferable upper limit is 5 % By weight. When the blending amount of the polyfunctional (meth) acrylate is less than 0.02% by weight, the acrylic copolymer is insufficiently cross-linked, and the resulting pressure-sensitive adhesive layer has reduced cohesion and processability. There are things to do. When the blending amount of the polyfunctional (meth) acrylate is more than 5% by weight, the pressure-sensitive adhesive layer obtained may have reduced adhesive strength and initial adhesiveness to the adherend, resulting in reduced reliability.
As for the compounding quantity of the said polyfunctional (meth) acrylate, the more preferable minimum in the said mixed monomer is 0.05 weight%, and a more preferable upper limit is 3 weight%.
上記光重合開始剤は特に限定されず、例えば、4-(2-ヒドロキシエトキシ)フェニル(2-ヒドロキシ-2-プロピル)ケトン(メルク社製、商品名「ダロキュア2959」)等のケトン系光重合開始剤、α-ヒドロキシ-α,α’-ジメチル-アセトフェノン(メルク社製、商品名「ダロキュア1173」)、メトキシアセトフェン、2,2-ジメトキシ-2-フェニルアセトフェン(チバガイギー社製、商品名「イルガキュア651」)、2-ヒドロキシ-2-シクロヘキシルアセトフェノン(チバガイギー社製、商品名「イルガキュア184」)等のアセトフェノン系光重合開始剤、ベンジルジメチルケタール等のケタール系光重合開始剤、ハロゲン化ケトン、アシルホスフィノキシド、アシルホスフォナート等が挙げられる。 The photopolymerization initiator is not particularly limited, and examples thereof include ketone photopolymerization such as 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (trade name “Darocur 2959” manufactured by Merck). Initiator, α-hydroxy-α, α'-dimethyl-acetophenone (Merck, trade name “Darocur 1173”), methoxyacetophene, 2,2-dimethoxy-2-phenylacetophene (Ciba Geigy, trade name) "Irgacure 651"), 2-hydroxy-2-cyclohexyl acetophenone (product name "Irgacure 184" manufactured by Ciba Geigy Co., Ltd.), etc., ketal photopolymerization initiators such as benzyldimethyl ketal, halogenated ketones , Acyl phosphinoxide, acyl phosphonate and the like.
上記光重合開始剤の配合量は特に限定されないが、上記混合モノマー100重量部に対する好ましい下限が0.01重量部、好ましい上限が5重量部である。上記光重合開始剤の配合量が0.01重量部未満であると、上記混合モノマーの重合が不完全となり、得られる粘着剤層は、凝集力の低下が原因となって必要な物性が得られないことがある。上記光重合開始剤の配合量が5重量部を超えると、光照射時にラジカル発生量が多くなり、得られるアクリル共重合体の数平均分子量が低下したり、粘着剤層のゲル分率が低下したりすることにより、高温高湿下で生じる白化を充分に抑制することができないことがある。
上記光重合開始剤の配合量は、上記混合モノマー100重量部に対するより好ましい下限が0.03重量部、より好ましい上限が1重量部である。
Although the compounding quantity of the said photoinitiator is not specifically limited, The preferable minimum with respect to 100 weight part of said mixed monomers is 0.01 weight part, and a preferable upper limit is 5 weight part. When the blending amount of the photopolymerization initiator is less than 0.01 parts by weight, the polymerization of the mixed monomer becomes incomplete, and the obtained pressure-sensitive adhesive layer has the necessary physical properties due to a decrease in cohesive force. It may not be possible. If the blending amount of the photopolymerization initiator exceeds 5 parts by weight, the amount of radicals generated during light irradiation increases, the number average molecular weight of the resulting acrylic copolymer decreases, or the gel fraction of the pressure-sensitive adhesive layer decreases. As a result, whitening that occurs under high temperature and high humidity may not be sufficiently suppressed.
As for the compounding quantity of the said photoinitiator, the more preferable minimum with respect to 100 weight part of said mixed monomers is 0.03 weight part, and a more preferable upper limit is 1 weight part.
上記透明な合成樹脂フィルムは特に限定されず、例えば、ポリエチレンテレフタレートフィルム等が挙げられる。 The said transparent synthetic resin film is not specifically limited, For example, a polyethylene terephthalate film etc. are mentioned.
上記光照射に用いられるランプは特に限定されず、例えば、波長400nm以下に発光分布を有するランプ等が挙げられる。
上記波長400nm以下に発光分布を有するランプとして、例えば、低圧水銀ランプ、中圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、ケミカルランプ、ブラックライトランプ、マイクロウエーブ励起水銀ランプ、メタルハライドランプ等が挙げられる。なかでも、上記光重合開始剤の活性波長領域の光を効率よく発光するとともに、上記モノマー層に含まれる上記光重合開始剤以外の成分の光吸収が少なく、上記モノマー層の内部にまで光が充分に到達して上記混合モノマーを効果的に重合させることができることから、ケミカルランプが好ましい。
The lamp used for the light irradiation is not particularly limited, and examples thereof include a lamp having a light emission distribution at a wavelength of 400 nm or less.
Examples of the lamp having a light emission distribution at a wavelength of 400 nm or less include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp. It is done. Among these, the light in the active wavelength region of the photopolymerization initiator is efficiently emitted, and there is little light absorption of components other than the photopolymerization initiator contained in the monomer layer, so that light can enter the monomer layer. A chemical lamp is preferred because it can sufficiently reach and effectively polymerize the mixed monomer.
上記光照射における光照射強度は特に限定されず、得られるアクリル共重合体の重合度を左右する因子であることから、目的とするアクリル共重合体の重合度又は粘着剤層の性能等に合わせて、適宜調整される。
例えば、上記光重合開始剤としてアセトフェノン系光重合開始剤を用いた場合、該アセトフェノン系光重合開始剤の光分解に有効な波長領域の光照射強度は、0.1~100mW/cmであることが好ましい。なお、上記アセトフェノン系光重合開始剤の光分解に有効な波長領域は、光重合開始剤によって異なるが、通常、365nm~420nm程度である。
The light irradiation intensity in the above light irradiation is not particularly limited, and is a factor that affects the degree of polymerization of the resulting acrylic copolymer, so that it matches the degree of polymerization of the target acrylic copolymer or the performance of the pressure-sensitive adhesive layer. And adjusted as appropriate.
For example, when an acetophenone photopolymerization initiator is used as the photopolymerization initiator, the light irradiation intensity in the wavelength region effective for photolysis of the acetophenone photopolymerization initiator is 0.1 to 100 mW / cm 2 . It is preferable. The wavelength range effective for the photodecomposition of the acetophenone-based photopolymerization initiator is usually about 365 nm to 420 nm, although it varies depending on the photopolymerization initiator.
本発明の光学部材用粘着テープの用途は特に限定されず、種々の光学部材に対して適用することができる。なかでも、本発明の光学部材用粘着剤組成物の場合と同様に、本発明の光学部材用粘着テープを、携帯電話、携帯情報端末等の画像表示装置を製造する際に、画像表示装置の表面を保護するための保護板と、ディスプレイパネルとを貼り合わせるために用いたり、また、携帯電話、携帯情報端末等の入力装置を製造する際に、タッチパネルのポリカーボネート板又はアクリル板と、ディスプレイパネルとを貼り合わせるために用いたりすることが好ましい。 The application of the pressure-sensitive adhesive tape for optical members of the present invention is not particularly limited, and can be applied to various optical members. In particular, as in the case of the pressure-sensitive adhesive composition for optical members of the present invention, the pressure-sensitive adhesive tape for optical members of the present invention is used in the manufacture of image display devices such as mobile phones and portable information terminals. Used to attach a protective plate for protecting the surface and a display panel, or when manufacturing an input device such as a mobile phone or a portable information terminal, a polycarbonate plate or an acrylic plate of a touch panel, and a display panel It is preferable to use for bonding together.
本発明によれば、高温高湿下で生じる白化を抑制し、高信頼性を実現することのできる光学部材用粘着剤組成物を提供することができる。また、本発明によれば、該光学部材用粘着剤組成物を用いて製造される光学部材用粘着テープを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the whitening which arises under high temperature and high humidity can be suppressed, and the adhesive composition for optical members which can implement | achieve high reliability can be provided. Moreover, according to this invention, the adhesive tape for optical members manufactured using this adhesive composition for optical members can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
(実施例1-1)
(1)アクリル共重合体の製造
温度計、攪拌機、冷却管を備えた反応器内に、2-エチルヘキシルアクリレート44.5 重量部と、イソボルニルアクリレート30重量部と、アクリル酸0.5重量部と、2-ヒドロキシエチルアクリレート25重量部と、これらモノマー100重量部に対して酢酸エチル100重量部とを加え、窒素置換した後、反応器を加熱して還流を開始した。30分間後、モノマー100重量部に対して0.2重量部の重合開始剤としてのt-ヘキシルパーオキシピバレートを5重量部の酢酸エチルで希釈し、得られた重合開始剤溶液を上記反応器内に2時間かけて滴下添加した。その後、70℃にて、重合開始剤の添加開始から8時間還流させて、固形分50%のアクリル共重合体溶液を得た。
Example 1-1
(1) Production of acrylic copolymer In a reactor equipped with a thermometer, a stirrer, and a cooling tube, 44.5 parts by weight of 2-ethylhexyl acrylate, 30 parts by weight of isobornyl acrylate, and 0.5 parts by weight of acrylic acid Then, 25 parts by weight of 2-hydroxyethyl acrylate, and 100 parts by weight of ethyl acetate with respect to 100 parts by weight of these monomers were replaced with nitrogen, and then the reactor was heated to start refluxing. After 30 minutes, 0.2 parts by weight of t-hexylperoxypivalate as a polymerization initiator with respect to 100 parts by weight of the monomer was diluted with 5 parts by weight of ethyl acetate, and the resulting polymerization initiator solution was subjected to the above reaction. It was added dropwise to the vessel over 2 hours. Thereafter, the mixture was refluxed at 70 ° C. for 8 hours from the start of addition of the polymerization initiator to obtain an acrylic copolymer solution having a solid content of 50%.
得られたアクリル共重合体について、熱分解装置(フロンティア・ラボ社製、ダブルショットパイロライザー)、GC-MS装置(日本電子社製、Q-1000GC)、FT-IR(Thermo Fisher Scientific社製、NICOLET6700)及びNMR(日本電子社製、JNM-ECA400)を用いて、アクリル共重合体を構成する各モノマー由来の構成単位の割合(重量%)を測定した。得られた構成単位の割合(重量%)を表1に示した。
また、得られたアクリル共重合体について、カラムとしてWaters社製「2690 Separations Model」を用いて、GPC法によってポリスチレン換算による重量平均分子量を測定した。得られた重量平均分子量を表1に示した。
About the obtained acrylic copolymer, a thermal decomposition apparatus (manufactured by Frontier Laboratories, double shot pyrolyzer), GC-MS apparatus (manufactured by JEOL Ltd., Q-1000GC), FT-IR (manufactured by Thermo Fisher Scientific, Using NICOLET6700) and NMR (manufactured by JEOL Ltd., JNM-ECA400), the proportion (% by weight) of the structural units derived from the respective monomers constituting the acrylic copolymer was measured. Table 1 shows the proportion (% by weight) of the obtained structural units.
Moreover, about the obtained acrylic copolymer, the weight average molecular weight by polystyrene conversion was measured by GPC method using "2690 Separations Model" made from Waters as a column. The obtained weight average molecular weight is shown in Table 1.
(2)光学部材用粘着テープの製造
得られたアクリル共重合体100重量部に、架橋剤としてコロネートHX(日本ポリウレタン社製)を0.5重量部添加し、攪拌して、光学部材用粘着剤組成物を調製した。
得られた光学部材用粘着剤組成物を、離型ポリエチレンテレフタレートフィルムの離型処理面に塗工して厚み100μmの粘着剤層を形成し、得られた粘着剤層の上に、離型処理面が粘着剤層に接するようにして新たに用意した離型ポリエチレンテレフタレートフィルムを重ね合わせて積層体を得た。得られた積層体をゴムローラにより加圧することにより、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。
(2) Manufacture of pressure-sensitive adhesive tape for optical member To 100 parts by weight of the obtained acrylic copolymer, 0.5 part by weight of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) is added as a cross-linking agent, and stirred to be pressure-sensitive adhesive for optical member. An agent composition was prepared.
The obtained pressure-sensitive adhesive composition for optical members is applied to a release-treated surface of a release polyethylene terephthalate film to form a 100 μm-thick pressure-sensitive adhesive layer, and a release treatment is performed on the obtained pressure-sensitive adhesive layer. A newly prepared release polyethylene terephthalate film was laminated so that the surface was in contact with the adhesive layer to obtain a laminate. By pressing the obtained laminate with a rubber roller, a double-sided pressure-sensitive adhesive tape for an optical member having a release polyethylene terephthalate film attached on both sides was obtained.
(実施例1-2~1-5、比較例1-1~1-3)
アクリル共重合体のモノマー組成を変更することにより、表1に示す構成単位の割合(重量%)を有するアクリル共重合体を得たこと以外は、実施例1-1と同様にして、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。
(Examples 1-2 to 1-5, Comparative Examples 1-1 to 1-3)
The mold release was carried out in the same manner as in Example 1-1, except that the acrylic copolymer having the proportion (% by weight) shown in Table 1 was obtained by changing the monomer composition of the acrylic copolymer. A double-sided pressure-sensitive adhesive tape for an optical member having a polyethylene terephthalate film attached on both sides was obtained.
(実施例2-1)
(1)アクリル共重合体の製造
温度計、攪拌機、冷却管を備えた反応器内に、2-エチルヘキシルアクリレート59.5重量部と、イソボルニルアクリレート15重量部と、アクリル酸0.5重量部と、N-ビニルピロリドン25重量部と、これらモノマー100重量部に対して酢酸エチル100重量部とを加え、窒素バブリング置換した後、窒素フロー下で反応器を70℃にした。次いで、モノマー100重量部に対して0.2重量部の重合開始剤としてのt-ヘキシルパーオキシピバレートを、5重量部の酢酸エチルで希釈し、得られた重合開始剤溶液を上記反応器内に2時間かけて滴下添加した。反応中は反応温度を70℃に保持するように、加熱冷却により温度を制御した。重合開始剤の添加開始から8時間まで70℃にて反応を行い、その後、冷却して反応を終了させることにより、固形分50%のアクリル共重合体溶液を得た。
Example 2-1
(1) Production of acrylic copolymer In a reactor equipped with a thermometer, a stirrer, and a cooling tube, 59.5 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of isobornyl acrylate, and 0.5 parts by weight of acrylic acid And 25 parts by weight of N-vinylpyrrolidone and 100 parts by weight of ethyl acetate with respect to 100 parts by weight of these monomers were substituted by nitrogen bubbling, and then the reactor was brought to 70 ° C. under a nitrogen flow. Subsequently, 0.2 parts by weight of t-hexylperoxypivalate as a polymerization initiator is diluted with 5 parts by weight of ethyl acetate with respect to 100 parts by weight of the monomer, and the resulting polymerization initiator solution is diluted with the above reactor. The solution was added dropwise over 2 hours. During the reaction, the temperature was controlled by heating and cooling so that the reaction temperature was maintained at 70 ° C. The reaction was carried out at 70 ° C. for 8 hours from the start of the addition of the polymerization initiator, and then the reaction was terminated by cooling to obtain an acrylic copolymer solution having a solid content of 50%.
得られたアクリル共重合体について、熱分解装置(フロンティア・ラボ社製、ダブルショットパイロライザー)、GC-MS装置(日本電子社製、Q-1000GC)、FT-IR(Thermo Fisher Scientific社製、NICOLET6700)及びNMR(日本電子社製、JNM-ECA400)を用いて、アクリル共重合体を構成する各モノマー由来の構成単位の割合(重量%)を測定した。得られた構成単位の割合(重量%)を表2に示した。
また、得られたアクリル共重合体について、カラムとしてWaters社製「2690 Separations Model」を用いて、GPC法によってポリスチレン換算による重量平均分子量を測定した。得られた重量平均分子量を表2に示した。
About the obtained acrylic copolymer, a thermal decomposition apparatus (manufactured by Frontier Laboratories, double shot pyrolyzer), GC-MS apparatus (manufactured by JEOL Ltd., Q-1000GC), FT-IR (manufactured by Thermo Fisher Scientific, Using NICOLET6700) and NMR (manufactured by JEOL Ltd., JNM-ECA400), the proportion (% by weight) of the structural units derived from the respective monomers constituting the acrylic copolymer was measured. Table 2 shows the ratio (wt%) of the obtained structural units.
Moreover, about the obtained acrylic copolymer, the weight average molecular weight by polystyrene conversion was measured by GPC method using "2690 Separations Model" made from Waters as a column. The obtained weight average molecular weight is shown in Table 2.
(2)光学部材用粘着テープの製造
得られたアクリル共重合体100重量部に、架橋剤としてデナコールEX212(ナガセケムテックス社製)を1.0重量部添加し、攪拌して、光学部材用粘着剤組成物を調製した。
得られた光学部材用粘着剤組成物を、離型ポリエチレンテレフタレートフィルムの離型処理面に塗工して厚み100μmの粘着剤層を形成し、得られた粘着剤層の上に、離型処理面が粘着剤層に接するようにして新たに用意した離型ポリエチレンテレフタレートフィルムを重ね合わせて積層体を得た。得られた積層体をゴムローラにより加圧することにより、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。
(2) Manufacture of pressure-sensitive adhesive tape for optical member To 100 parts by weight of the obtained acrylic copolymer, 1.0 part by weight of Denacol EX212 (manufactured by Nagase ChemteX) is added as a cross-linking agent, and stirred for optical member A pressure-sensitive adhesive composition was prepared.
The obtained pressure-sensitive adhesive composition for optical members is applied to a release-treated surface of a release polyethylene terephthalate film to form a 100 μm-thick pressure-sensitive adhesive layer, and a release treatment is performed on the obtained pressure-sensitive adhesive layer. A newly prepared release polyethylene terephthalate film was laminated so that the surface was in contact with the adhesive layer to obtain a laminate. By pressing the obtained laminate with a rubber roller, a double-sided pressure-sensitive adhesive tape for an optical member having a release polyethylene terephthalate film attached on both sides was obtained.
(実施例2-2~2-8、比較例2-1~2-3)
アクリル共重合体のモノマー組成と反応時の酢酸エチルの量とを変更することにより、表2に示す構成単位の割合(重量%)と重量平均分子量とを有するアクリル共重合体を得たこと以外は、実施例2-1と同様にして、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。
(Examples 2-2 to 2-8, Comparative Examples 2-1 to 2-3)
By changing the monomer composition of the acrylic copolymer and the amount of ethyl acetate at the time of reaction, except that the acrylic copolymer having the proportion (% by weight) of the structural units and the weight average molecular weight shown in Table 2 was obtained. In the same manner as in Example 2-1, a double-sided pressure-sensitive adhesive tape for an optical member having a release polyethylene terephthalate film attached on both sides was obtained.
(実施例3-1)
(1)アクリル共重合体の製造
温度計、攪拌機、冷却管を備えた反応器内に、2-エチルヘキシルアクリレート59.3重量部と、イソボルニルアクリレート35重量部と、アクリル酸0.5重量部と、2-ヒドロキシエチルアクリレート0.2重量部と、一般式(1-1)で表される構造を有するモノマーとしてブレンマーPME-1000(エチレンオキサイドの繰り返し数=23、末端メチル基、日油社製)5重量部と、これらモノマー100重量部に対して酢酸エチル100重量部とを加え、窒素置換した後、反応器を加熱して還流を開始した。30分後、モノマー100重量部に対して0.2重量部の重合開始剤としてのt-ヘキシルパーオキシピバレートを5重量部の酢酸エチルで希釈し、得られた重合開始剤溶液を上記反応器内に2時間かけて滴下添加した。その後、70℃にて、重合開始剤の添加開始から8時間還流させて、固形分50%のアクリル共重合体溶液を得た。
Example 3-1
(1) Production of acrylic copolymer In a reactor equipped with a thermometer, a stirrer, and a cooling pipe, 59.3 parts by weight of 2-ethylhexyl acrylate, 35 parts by weight of isobornyl acrylate, and 0.5 parts by weight of acrylic acid And 0.2 parts by weight of 2-hydroxyethyl acrylate, as a monomer having a structure represented by the general formula (1-1), BLEMMER PME-1000 (ethylene oxide repeat number = 23, terminal methyl group, NOF 5 parts by weight) and 100 parts by weight of ethyl acetate to 100 parts by weight of these monomers were added and purged with nitrogen, and then the reactor was heated to start refluxing. After 30 minutes, 0.2 parts by weight of t-hexylperoxypivalate as a polymerization initiator with respect to 100 parts by weight of the monomer was diluted with 5 parts by weight of ethyl acetate, and the resulting polymerization initiator solution was subjected to the above reaction. It was added dropwise to the vessel over 2 hours. Thereafter, the mixture was refluxed at 70 ° C. for 8 hours from the start of addition of the polymerization initiator to obtain an acrylic copolymer solution having a solid content of 50%.
また、得られたアクリル共重合体について、カラムとしてWaters社製「2690 Separations Model」を用いて、GPC法によってポリスチレン換算による重量平均分子量を測定した。得られた重量平均分子量を表3に示した。 Moreover, about the obtained acrylic copolymer, the weight average molecular weight by polystyrene conversion was measured by GPC method using "2690 Separations Model" made from Waters as a column. The obtained weight average molecular weight is shown in Table 3.
(2)光学部材用粘着テープの製造
得られたアクリル共重合体100重量部に、架橋剤としてコロネートHX(日本ポリウレタン社製)を0.5重量部添加し、攪拌して、光学部材用粘着剤組成物を調製した。
得られた光学部材用粘着剤組成物を、離型ポリエチレンテレフタレートフィルムの離型処理面に塗工して厚み100μmの粘着剤層を形成し、得られた粘着剤層の上に、離型処理面が粘着剤層に接するようにして新たに用意した離型ポリエチレンテレフタレートフィルムを重ね合わせて積層体を得た。得られた積層体をゴムローラにより加圧することにより、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。
(2) Manufacture of pressure-sensitive adhesive tape for optical member To 100 parts by weight of the obtained acrylic copolymer, 0.5 part by weight of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) is added as a cross-linking agent, and stirred to be pressure-sensitive adhesive for optical member. An agent composition was prepared.
The obtained pressure-sensitive adhesive composition for optical members is applied to a release-treated surface of a release polyethylene terephthalate film to form a 100 μm-thick pressure-sensitive adhesive layer, and a release treatment is performed on the obtained pressure-sensitive adhesive layer. A newly prepared release polyethylene terephthalate film was laminated so that the surface was in contact with the adhesive layer to obtain a laminate. By pressing the obtained laminate with a rubber roller, a double-sided pressure-sensitive adhesive tape for an optical member having a release polyethylene terephthalate film attached on both sides was obtained.
(実施例3-2~3-9、比較例3-1~3-5)
アクリル共重合体のモノマー組成を表3又は4に示すように変更することにより、表3又は4に示す重量平均分子量を有するアクリル共重合体を得たこと以外は、実施例3-1と同様にして、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。
(Examples 3-2 to 3-9, Comparative Examples 3-1 to 3-5)
Similar to Example 3-1, except that the acrylic copolymer having the weight average molecular weight shown in Table 3 or 4 was obtained by changing the monomer composition of the acrylic copolymer as shown in Table 3 or 4. Thus, a double-sided pressure-sensitive adhesive tape for optical members having a release polyethylene terephthalate film attached on both sides was obtained.
(実施例3-10)
2-エチルヘキシルアクリレート59.4重量部と、イソボルニルアクリレート35重量部と、アクリル酸0.5重量部と、一般式(1-1)で表される構造を有するモノマーとしてブレンマーPME-1000(エチレンオキサイドの繰り返し数=23、末端メチル基、日油社製)5重量部と、1,6-ヘキサンジオールジアクリレート0.1重量部と、2,2-ジメトキシ-2-フェニルアセトフェン(チバガイギー社製、商品名「イルガキュア651」)とを均一に混合した後、窒素パージすることにより、溶存酸素が除去されたモノマー組成物を作製した。
(Example 3-10)
As a monomer having a structure represented by the general formula (1-1), 59.4 parts by weight of 2-ethylhexyl acrylate, 35 parts by weight of isobornyl acrylate, 0.5 parts by weight of acrylic acid, and BLEMMER PME-1000 ( Number of ethylene oxide repeats = 23, terminal methyl group, manufactured by NOF Corporation), 5 parts by weight of 1,6-hexanediol diacrylate, 2,2-dimethoxy-2-phenylacetophene (Ciba Geigy) A monomer composition from which dissolved oxygen was removed was produced by uniformly purging with a product name “Irgacure 651” manufactured by the company, and then purging with nitrogen.
得られたモノマー組成物を、厚みが100μmとなるように100μmのスペーサーを介して、厚み38μmのシリコン離型ポリエチレンテレフタレートフィルム2枚に、各々の離型処理面がモノマー組成物と接するように挟んだ。次いで、主波長365nmの蛍光ランプを用い、モノマー組成物に2mWの紫外線を5分間照射してモノマーを重合することにより、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。 The obtained monomer composition was sandwiched between two silicon release polyethylene terephthalate films having a thickness of 38 μm through two spacers having a thickness of 100 μm so that the thickness would be 100 μm so that each release treatment surface was in contact with the monomer composition. It is. Next, a double-sided pressure-sensitive adhesive tape for an optical member having a release polyethylene terephthalate film attached to both sides is obtained by polymerizing the monomer by irradiating the monomer composition with 2 mW ultraviolet rays for 5 minutes using a fluorescent lamp having a dominant wavelength of 365 nm. Obtained.
なお、重合と同時に架橋構造が形成されることから、得られたアクリル共重合体の重量平均分子量を測定することは困難である。 In addition, since a crosslinked structure is formed simultaneously with polymerization, it is difficult to measure the weight average molecular weight of the obtained acrylic copolymer.
(実施例3-11~3-18、比較例3-6~3-10)
アクリル共重合体のモノマー組成を表5又は6に示すように変更してアクリル共重合体を得たこと以外は、実施例3-10と同様にして、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。
(Examples 3-11 to 3-18, Comparative Examples 3-6 to 3-10)
A release polyethylene terephthalate film was applied to both sides in the same manner as in Example 3-10, except that the acrylic copolymer was obtained by changing the monomer composition of the acrylic copolymer as shown in Table 5 or 6. The obtained double-sided pressure-sensitive adhesive tape for optical members was obtained.
(実施例4-1)
(1)アクリル共重合体の製造
温度計、攪拌機、冷却管を備えた反応器内に、2-エチルヘキシルアクリレート59.3重量部と、イソボルニルアクリレート35重量部と、アクリル酸0.5重量部と、2-ヒドロキシエチルアクリレート0.2重量部と、一般式(1-2)で表される構造を有するモノマーとしてブレンマーPSE-1300(エチレンオキサイドの繰り返し数=30、末端オクタデシル基、日油社製)5重量部と、これらモノマー100重量部に対して酢酸エチル100重量部とを加え、窒素置換した後、反応器を加熱して還流を開始した。30分後、モノマー100重量部に対して0.2重量部の重合開始剤としてのt-ヘキシルパーオキシピバレートを5重量部の酢酸エチルで希釈し、得られた重合開始剤溶液を上記反応器内に2時間かけて滴下添加した。その後、70℃にて、重合開始剤の添加開始から8時間還流させて、固形分50%のアクリル共重合体溶液を得た。
Example 4-1
(1) Production of acrylic copolymer In a reactor equipped with a thermometer, a stirrer, and a cooling pipe, 59.3 parts by weight of 2-ethylhexyl acrylate, 35 parts by weight of isobornyl acrylate, and 0.5 parts by weight of acrylic acid And 0.2 parts by weight of 2-hydroxyethyl acrylate, and as a monomer having a structure represented by the general formula (1-2), BLEMMER PSE-1300 (ethylene oxide repeat number = 30, terminal octadecyl group, NOF) 5 parts by weight) and 100 parts by weight of ethyl acetate to 100 parts by weight of these monomers were added and purged with nitrogen, and then the reactor was heated to start refluxing. After 30 minutes, 0.2 parts by weight of t-hexylperoxypivalate as a polymerization initiator with respect to 100 parts by weight of the monomer was diluted with 5 parts by weight of ethyl acetate, and the resulting polymerization initiator solution was subjected to the above reaction. It was added dropwise to the vessel over 2 hours. Thereafter, the mixture was refluxed at 70 ° C. for 8 hours from the start of addition of the polymerization initiator to obtain an acrylic copolymer solution having a solid content of 50%.
得られたアクリル共重合体について、カラムとしてWaters社製「2690 Separations Model」を用いて、GPC法によってポリスチレン換算による重量平均分子量を測定した。得られた重量平均分子量を表7に示した。 About the obtained acrylic copolymer, the weight average molecular weight by polystyrene conversion was measured by GPC method using "2690 Separations Model" made from Waters as a column. The obtained weight average molecular weight is shown in Table 7.
(2)光学部材用粘着テープの製造
得られたアクリル共重合体100重量部に、架橋剤としてコロネートHX(日本ポリウレタン社製)を0.5重量部添加し、攪拌して、光学部材用粘着剤組成物を調製した。
得られた光学部材用粘着剤組成物を、離型ポリエチレンテレフタレートフィルムの離型処理面に塗工して厚み100μmの粘着剤層を形成し、得られた粘着剤層の上に、離型処理面が粘着剤層に接するようにして新たに用意した離型ポリエチレンテレフタレートフィルムを重ね合わせて積層体を得た。得られた積層体をゴムローラにより加圧することにより、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。
(2) Manufacture of pressure-sensitive adhesive tape for optical member To 100 parts by weight of the obtained acrylic copolymer, 0.5 part by weight of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) is added as a cross-linking agent, and stirred to be pressure-sensitive adhesive for optical member. An agent composition was prepared.
The obtained pressure-sensitive adhesive composition for optical members is applied to a release-treated surface of a release polyethylene terephthalate film to form a 100 μm-thick pressure-sensitive adhesive layer, and a release treatment is performed on the obtained pressure-sensitive adhesive layer. A newly prepared release polyethylene terephthalate film was laminated so that the surface was in contact with the adhesive layer to obtain a laminate. By pressing the obtained laminate with a rubber roller, a double-sided pressure-sensitive adhesive tape for an optical member having a release polyethylene terephthalate film attached on both sides was obtained.
(実施例4-2~4-9、比較例4-1)
アクリル共重合体のモノマー組成を表7に示すように変更することにより、表7に示す重量平均分子量を有するアクリル共重合体を得たこと以外は、実施例4-1と同様にして、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。
(Examples 4-2 to 4-9, Comparative Example 4-1)
In the same manner as in Example 4-1, except that the acrylic copolymer having the weight average molecular weight shown in Table 7 was obtained by changing the monomer composition of the acrylic copolymer as shown in Table 7. A double-sided pressure-sensitive adhesive tape for optical members having a polyethylene terephthalate film attached on both sides was obtained.
(実施例4-10)
2-エチルヘキシルアクリレート59.4重量部と、イソボルニルアクリレート35重量部と、アクリル酸0.5重量部と、一般式(1-2)で表される構造を有するモノマーとしてブレンマーPSE-1300(エチレンオキサイドの繰り返し数=30、末端オクタデシル基、日油社製)5重量部と、1,6-ヘキサンジオールジアクリレート0.1重量部と、2,2-ジメトキシ-2-フェニルアセトフェン(チバガイギー社製、商品名「イルガキュア651」)とを均一に混合した後、窒素パージすることにより、溶存酸素が除去されたモノマー組成物を作製した。
(Example 4-10)
Blemmer PSE-1300 (monomer having a structure represented by the general formula (1-2), 59.4 parts by weight of 2-ethylhexyl acrylate, 35 parts by weight of isobornyl acrylate, 0.5 part by weight of acrylic acid, Number of ethylene oxide repeats = 30, terminal octadecyl group, manufactured by NOF Corporation), 0.1 part by weight of 1,6-hexanediol diacrylate, 2,2-dimethoxy-2-phenylacetophene (Ciba-Geigy) A monomer composition from which dissolved oxygen was removed was produced by uniformly purging with a product name “Irgacure 651” manufactured by the company, and then purging with nitrogen.
得られたモノマー組成物を、厚みが100μmとなるように100μmのスペーサーを介して、厚み38μmのシリコン離型ポリエチレンテレフタレートフィルム2枚に、各々の離型処理面がモノマー組成物と接するように挟んだ。次いで、主波長365nmの蛍光ランプを用い、モノマー組成物に2mWの紫外線を5分間照射してモノマーを重合することにより、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。 The obtained monomer composition was sandwiched between two silicon release polyethylene terephthalate films having a thickness of 38 μm through two spacers having a thickness of 100 μm so that the thickness would be 100 μm so that each release treatment surface was in contact with the monomer composition. It is. Next, a double-sided pressure-sensitive adhesive tape for an optical member having a release polyethylene terephthalate film attached to both sides is obtained by polymerizing the monomer by irradiating the monomer composition with 2 mW ultraviolet rays for 5 minutes using a fluorescent lamp having a dominant wavelength of 365 nm. Obtained.
なお、重合と同時に架橋構造が形成されることから、得られたアクリル共重合体の重量平均分子量を測定することは困難である。 In addition, since a crosslinked structure is formed simultaneously with polymerization, it is difficult to measure the weight average molecular weight of the obtained acrylic copolymer.
(実施例4-11~4-18、比較例4-2)
アクリル共重合体のモノマー組成を表8に示すように変更してアクリル共重合体を得たこと以外は、実施例4-10と同様にして、離型ポリエチレンテレフタレートフィルムが両面に貼り付けられた光学部材用両面粘着テープを得た。
(Examples 4-11 to 4-18, Comparative Example 4-2)
A release polyethylene terephthalate film was attached to both sides in the same manner as in Example 4-10, except that the acrylic copolymer was obtained by changing the monomer composition of the acrylic copolymer as shown in Table 8. A double-sided pressure-sensitive adhesive tape for optical members was obtained.
(評価)
実施例及び比較例で得られた光学部材用両面粘着テープについて、下記のような評価を行った。結果を表1~8に示した。
(Evaluation)
The following evaluation was performed about the double-sided adhesive tape for optical members obtained by the Example and the comparative example. The results are shown in Tables 1-8.
(1)ゲル分率の測定
得られた光学部材用両面粘着テープの片面から離型ポリエチレンテレフタレートフィルムを剥がし、光学部材用両面粘着テープである粘着剤層をスプーンを使ってかきとって粘着剤の塊を作製し、粘着剤の塊の重量Wを測定した。粘着剤の塊を酢酸エチル中に23℃にて24時間浸漬した後、200メッシュのステンレスメッシュを介して粘着剤の塊を酢酸エチルから取り出して、110℃の条件下で1時間乾燥させた。乾燥後の粘着剤の塊の重量Wを測定し、式(1)によりゲル分率を算出した。
(1) Measurement of gel fraction Peel off the release polyethylene terephthalate film from one side of the obtained double-sided pressure-sensitive adhesive tape for optical members, and scrape off the pressure-sensitive adhesive layer, which is a double-sided pressure-sensitive adhesive tape for optical members, using a spoon. A lump was prepared, and the weight W 1 of the lump of the adhesive was measured. After the pressure-sensitive adhesive lump was immersed in ethyl acetate at 23 ° C. for 24 hours, the pressure-sensitive adhesive lump was taken out from ethyl acetate through a 200-mesh stainless steel mesh and dried at 110 ° C. for 1 hour. The weight W 2 of the mass after drying of the adhesive was measured to calculate the gel fraction by the equation (1).
(2)白化の発生評価(ヘーズ値の測定)
得られた光学部材用両面粘着テープの両面から離型ポリエチレンテレフタレートフィルムを剥がし、片面の表面に透明なポリエチレンテレフタレートフィルムを貼り付け、他方の表面にスライドガラス(商品名「S-1214」、MATSUNAMI社製)を貼り付けて、透明なポリエチレンテレフタレートフィルム/光学部材用両面粘着テープである粘着剤層/スライドガラスの三層構造を有する試験片を作製した。試験片の作製直後のヘーズ値(%)、及び、この試験片を80℃85%RHの高温高湿下に24時間放置した後の試験片のヘーズ値(%)を、ヘーズメーター(全自動ヘーズメーター「TC-HIIIDPK」、東京電色社製)を用いて測定し、下記式(2)によりΔヘーズ値を算出した。    
Δヘーズ値(%)={24時間放置した後の試験片のヘーズ値(%)}-{試験片の作製直後のヘーズ値(%)} (2)
(2) Evaluation of occurrence of whitening (measurement of haze value)
The release polyethylene terephthalate film is peeled off from both sides of the obtained double-sided pressure-sensitive adhesive tape for optical members, a transparent polyethylene terephthalate film is pasted on one surface, and a slide glass (trade name “S-1214”, MATSANAMI Corporation) is attached to the other surface. A test piece having a three-layer structure of transparent polyethylene terephthalate film / double-sided pressure-sensitive adhesive tape for optical members / adhesive layer / slide glass was prepared. The haze value (%) immediately after the preparation of the test piece and the haze value (%) of the test piece after leaving the test piece under high temperature and high humidity of 80 ° C. and 85% RH for 24 hours are expressed as a haze meter (fully automatic). Using a haze meter “TC-HIIIDPK” (manufactured by Tokyo Denshoku), Δ haze value was calculated by the following formula (2).
Δhaze value (%) = {haze value of test piece after standing for 24 hours (%)} − {haze value immediately after preparation of test piece (%)} (2)
(3)粘着力評価
得られた光学部材用両面粘着テープを25mm×100mmの平面形状を有するように切断した。切断した光学部材用両面粘着テープの一方の離型ポリエチレンテレフタレートフィルムを剥離し、光学部材用両面粘着テープの露出した面をポリエチレンテレフタレートフィルム上に貼り合わせた。更に、光学部材用両面粘着テープのもう一方の離型ポリエチレンテレフタレートフィルムを剥離し、光学部材用両面粘着テープの露出した面をポリカーボネート板(PC板)上に貼り合わせることにより、ポリカーボネート板(PC板)上に、光学部材用両面粘着テープとポリエチレンテレフタレートフィルムとがこの順で積層されている積層サンプルを得た。その後、得られた積層サンプルのポリエチレンテレフタレートフィルム上に2.0kgのゴムローラを載せて、300mm/分の速度でゴムローラを一往復させることにより、ポリカーボネート板(PC板)と光学部材用両面粘着テープとを貼り合わせ、23℃で20分間放置し、試験サンプルを用意した。
得られた試験サンプルについて、JIS Z0237に準じて、剥離速度300mm/分で180°方向の引張試験を行い、初期粘着力(N/25mm)を測定した。また、得られた試験サンプルを23℃で24時間放置した後、JIS Z0237に準じて、剥離速度300mm/分で180°方向の引張試験を行い、24時間後の粘着力(N/25mm)を測定した。
(3) Evaluation of adhesive strength The obtained double-sided adhesive tape for optical members was cut so as to have a planar shape of 25 mm × 100 mm. One release polyethylene terephthalate film of the cut double-sided pressure-sensitive adhesive tape for optical members was peeled, and the exposed surface of the double-sided pressure-sensitive adhesive tape for optical members was bonded onto the polyethylene terephthalate film. Further, the other release polyethylene terephthalate film of the double-sided pressure-sensitive adhesive tape for optical members is peeled off, and the exposed surface of the double-sided pressure-sensitive adhesive tape for optical members is bonded onto the polycarbonate plate (PC plate), whereby a polycarbonate plate (PC plate) ) To obtain a laminated sample in which a double-sided pressure-sensitive adhesive tape for an optical member and a polyethylene terephthalate film are laminated in this order. Thereafter, a 2.0 kg rubber roller is placed on the polyethylene terephthalate film of the obtained laminated sample, and the rubber roller is reciprocated once at a speed of 300 mm / min. And left at 23 ° C. for 20 minutes to prepare a test sample.
The obtained test sample was subjected to a tensile test in the 180 ° direction at a peeling speed of 300 mm / min according to JIS Z0237, and the initial adhesive strength (N / 25 mm) was measured. The obtained test sample was allowed to stand at 23 ° C. for 24 hours, and then subjected to a tensile test in the 180 ° direction at a peeling rate of 300 mm / min according to JIS Z0237, and the adhesive strength (N / 25 mm) after 24 hours was measured. It was measured.
(4)気泡発生状態(耐発泡性試験)
得られた光学部材用両面粘着テープを45mm×60mmの平面形状を有するように裁断した。裁断された光学部材用両面粘着テープの一方の離型ポリエチレンテレフタレートフィルムを剥離し、光学部材用両面粘着テープの露出した面を厚みが0.5mmのポリエチレンテレフタレートフィルム上に貼り合わせた。更に、光学部材用両面粘着テープのもう一方の離型ポリエチレンテレフタレートフィルムを剥離し、光学部材用両面粘着テープの露出した面を厚みが2.0mmの平面形状を有するポリカーボネート板(PC板)上に貼り合わせることにより、ポリカーボネート板(PC板)上に、光学部材用両面粘着テープとポリエチレンテレフタレートフィルムとがこの順で積層されている積層サンプルを得た。その後、得られた積層サンプルを温度85℃の条件、又は、温度60℃かつ相対湿度(RH)90%の条件で24時間静置し、試験サンプルを得た。得られた試験サンプルの接着界面における気泡発生状態を目視により観察した。
0.01mm以上の大きさの気泡が全く観察されなかった場合を「〇」と、0.01mm以上の大きさの気泡が1つの試験サンプル当たり1~5個観察された場合を「△」と、0.01mm以上の大きさの気泡が1つの試験サンプル当たり6個以上観察された場合を「×」として、気泡発生状態を評価した。
(4) Bubble generation state (foam resistance test)
The obtained double-sided pressure-sensitive adhesive tape for optical members was cut so as to have a flat shape of 45 mm × 60 mm. One release polyethylene terephthalate film of the cut double-sided pressure-sensitive adhesive tape for optical members was peeled, and the exposed surface of the double-sided pressure-sensitive adhesive tape for optical members was bonded onto a polyethylene terephthalate film having a thickness of 0.5 mm. Furthermore, the other release polyethylene terephthalate film of the double-sided pressure-sensitive adhesive tape for optical members is peeled, and the exposed surface of the double-sided pressure-sensitive adhesive tape for optical members is placed on a polycarbonate plate (PC plate) having a planar shape with a thickness of 2.0 mm. By laminating, a laminated sample in which a double-sided pressure-sensitive adhesive tape for optical members and a polyethylene terephthalate film were laminated in this order on a polycarbonate plate (PC plate) was obtained. Thereafter, the obtained laminated sample was allowed to stand for 24 hours under the condition of a temperature of 85 ° C. or a temperature of 60 ° C. and a relative humidity (RH) of 90% to obtain a test sample. The bubble generation state in the adhesion interface of the obtained test sample was visually observed.
“◯” indicates that no bubbles having a size of 0.01 mm or more were observed, and “△” indicates that 1 to 5 bubbles having a size of 0.01 mm or more were observed per test sample. The bubble generation state was evaluated by setting “x” when 6 or more bubbles having a size of 0.01 mm or more were observed per test sample.
(5)ITO膜に貼り付けた際の白化の有無
得られた光学部材用両面粘着テープの両面から離型ポリエチレンテレフタレートフィルムを剥がし、片面の表面にITO膜を貼り付け、他方の表面にスライドガラス(商品名「S-1214」、MATSUNAMI社製)を貼り付けて、ITO膜/光学部材用両面粘着テープである粘着剤層/スライドガラスの三層構造を有する試験片を作製した。この試験片を80℃85%RHの高温高湿下に放置し、試験片の作製直後のヘーズ値(%)、及び、24時間放置後の試験片のヘーズ値(%)を、ヘーズメーター(全自動ヘーズメーター「TC-HIIIDPK」、東京電色社製)を用いて測定し、上記式(2)によりΔヘーズ値を算出した。Δヘーズ値が、0.2未満であった場合を「◎」と、0.2以上3未満であった場合を「○」と、3以上4未満であった場合を「△」と、4以上であった場合を「×」として評価した。
(5) Presence or absence of whitening when pasted on the ITO film Peel the release polyethylene terephthalate film from both sides of the obtained double-sided adhesive tape for optical members, paste the ITO film on one surface, and slide glass on the other surface (Trade name “S-1214”, manufactured by MATSUNAMI) was attached to prepare a test piece having a three-layer structure of an adhesive layer / slide glass which is an ITO film / double-sided adhesive tape for optical members. The test piece was left under high temperature and high humidity of 80 ° C. and 85% RH, and the haze value (%) immediately after the preparation of the test piece and the haze value (%) of the test piece after 24 hours were measured. Measurement was performed using a fully automatic haze meter “TC-HIIIDPK” (manufactured by Tokyo Denshoku Co., Ltd.), and a Δhaze value was calculated by the above formula (2). When the Δhaze value is less than 0.2, “「 ”, when it is 0.2 or more and less than 3,“ ◯ ”, when it is 3 or more and less than 4,“ Δ ”, 4 The case where it was above was evaluated as "x".
(6)ITO膜間の抵抗評価
得られた光学部材用両面粘着テープを長さ40mm×幅60mmの平面形状を有するように裁断した。更に、幅方向で隣り合う2つの角を、それぞれ、角からの長さ10mm、角からの幅10mmのサイズの平面形状で切断し、凸状のテープシートを得た。凸状のテープシートの一方の離型ポリエチレンテレフタレートフィルムを剥離し、凸状のテープシートの露出した面をポリエチレンテレフタレート上に貼り合わせた。更に、凸状のテープシートのもう一方の離型ポリエチレンテレフタレートフィルムを剥離し、凸状のテープシートの露出した面を長さ40mm×幅60mmの平面形状を有するITOフィルムのITO膜面上に貼り合わせることにより、ITOフィルムのITO膜面上に、光学部材用両面粘着テープとポリエチレンテレフタレートとがこの順で積層されている導電性フィルム積層体を得た。
その後、得られた導電性フィルム積層体の初期抵抗値を測定した。また、導電性フィルム積層体を60℃及び相対湿度90%RHの高温高湿下で100時間放置し、非晶質ITO膜(尾池工業社製)を用いて、放置後の導電性フィルム積層体の抵抗値を測定した。なお、2端子抵抗値測定器の端子を10mm×10mmのサイズのITO膜面の露出面に当てて、抵抗値を測定した。
下記式(3)より算出される抵抗値変化率を用いて、ITOの劣化レベルを評価した。
抵抗値変化率(%)=(R-R)/R×100  (3)
式(3)中、Rは初期抵抗値を表し、Rは高温高湿下で100時間放置した後の抵抗値を表す。
(6) Resistance evaluation between ITO films The obtained double-sided pressure-sensitive adhesive tape for optical members was cut so as to have a planar shape of length 40 mm × width 60 mm. Further, two corners adjacent in the width direction were cut into a planar shape having a length of 10 mm from the corner and a width of 10 mm from the corner to obtain a convex tape sheet. One release polyethylene terephthalate film of the convex tape sheet was peeled off, and the exposed surface of the convex tape sheet was bonded onto polyethylene terephthalate. Further, the other release polyethylene terephthalate film of the convex tape sheet is peeled off, and the exposed surface of the convex tape sheet is pasted on the ITO film surface of the ITO film having a planar shape of length 40 mm × width 60 mm. By combining, the conductive film laminated body by which the double-sided adhesive tape for optical members and the polyethylene terephthalate were laminated | stacked in this order on the ITO film | membrane surface of an ITO film was obtained.
Then, the initial resistance value of the obtained electroconductive film laminated body was measured. Also, the conductive film laminate is allowed to stand for 100 hours at a high temperature and high humidity of 60 ° C. and a relative humidity of 90% RH, and an amorphous ITO film (manufactured by Oike Kogyo Co., Ltd.) is used to leave the conductive film laminate. The resistance value of the body was measured. The resistance value was measured by placing the terminal of the two-terminal resistance value measuring device on the exposed surface of the ITO film having a size of 10 mm × 10 mm.
The deterioration level of ITO was evaluated using the resistance value change rate calculated from the following formula (3).
Resistance value change rate (%) = (R 1 −R 0 ) / R 0 × 100 (3)
In the formula (3), R 0 represents an initial resistance value, and R 1 represents a resistance value after being left for 100 hours under high temperature and high humidity.
なお、抵抗値変化率は20%以下であることが好ましく、15%以下であることがより好ましい。抵抗値変化率が20%を超えると、ITO膜を有するタッチパネルの認識部位に誤った電気信号が入力され、応答に弊害を引き起こすことがある。 The resistance value change rate is preferably 20% or less, and more preferably 15% or less. If the resistance value change rate exceeds 20%, an erroneous electric signal may be input to the recognition part of the touch panel having the ITO film, which may cause a bad response.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
本発明によれば、高温高湿下で生じる白化を抑制し、高信頼性を実現することのできる光学部材用粘着剤組成物を提供することができる。また、本発明によれば、該光学部材用粘着剤組成物を用いて製造される光学部材用粘着テープを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the whitening which arises under high temperature and high humidity can be suppressed, and the adhesive composition for optical members which can implement | achieve high reliability can be provided. Moreover, according to this invention, the adhesive tape for optical members manufactured using this adhesive composition for optical members can be provided.

Claims (11)

  1. アクリル共重合体を含有する光学部材用粘着剤組成物であって、
    前記アクリル共重合体は、2-ヒドロキシエチルアクリレート1~25重量%、N-ビニルピロリドン1~25重量%、下記一般式(1-1)で表される構造を有するモノマー0.5~30重量%、又は、下記一般式(1-2)で表される構造を有するモノマー0.1~30重量%を含有する混合モノマーを重合することにより得られる
    ことを特徴とする光学部材用粘着剤組成物。 
    Figure JPOXMLDOC01-appb-C000001
    一般式(1-1)中、Rは水素原子又はメチル基を表し、Rは水素原子又は炭素数3未満のアルキル基を表し、nは8~45の整数を表す。
    Figure JPOXMLDOC01-appb-C000002
    一般式(1-2)中、Rは水素原子又はメチル基を表し、Rは炭素数3~30のアルキル基を表し、mは8~45の整数を表す。
    An adhesive composition for an optical member containing an acrylic copolymer,
    The acrylic copolymer is composed of 1 to 25% by weight of 2-hydroxyethyl acrylate, 1 to 25% by weight of N-vinylpyrrolidone, and 0.5 to 30% by weight of a monomer having a structure represented by the following general formula (1-1) %, Or a mixed monomer containing 0.1 to 30% by weight of a monomer having a structure represented by the following general formula (1-2). object.
    Figure JPOXMLDOC01-appb-C000001
    In general formula (1-1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or an alkyl group having less than 3 carbon atoms, and n represents an integer of 8 to 45.
    Figure JPOXMLDOC01-appb-C000002
    In general formula (1-2), R 3 represents a hydrogen atom or a methyl group, R 4 represents an alkyl group having 3 to 30 carbon atoms, and m represents an integer of 8 to 45.
  2. アクリル共重合体は、一般式(1-1)で表される構造を有するモノマー0.5~30重量%、又は、一般式(1-2)で表される構造を有するモノマー0.1~30重量%を含有する混合モノマーを重合することにより得られることを特徴とする請求項1記載の光学部材用粘着剤組成物。 The acrylic copolymer is 0.5 to 30% by weight of the monomer having the structure represented by the general formula (1-1), or 0.1 to 0.1% of the monomer having the structure represented by the general formula (1-2). The pressure-sensitive adhesive composition for an optical member according to claim 1, wherein the pressure-sensitive adhesive composition is obtained by polymerizing a mixed monomer containing 30% by weight.
  3. アクリル共重合体は、一般式(1-2)で表される構造を有するモノマー0.1~30重量%を含有する混合モノマーを重合することにより得られることを特徴とする請求項2記載の光学部材用粘着剤組成物。 The acrylic copolymer is obtained by polymerizing a mixed monomer containing 0.1 to 30% by weight of a monomer having a structure represented by the general formula (1-2). An adhesive composition for optical members.
  4. 一般式(1-2)中、Rは水素原子又はメチル基であり、Rは炭素数18のアルキル基であり、mは30であることを特徴とする請求項3記載の光学部材用粘着剤組成物。 4. The optical member according to claim 3 , wherein, in the general formula (1-2), R 3 is a hydrogen atom or a methyl group, R 4 is an alkyl group having 18 carbon atoms, and m is 30. Adhesive composition.
  5. アクリル共重合体は、重量平均分子量が20万~150万であることを特徴とする請求項1、2、3又は4記載の光学部材用粘着剤組成物。 The pressure-sensitive adhesive composition for optical members according to claim 1, 2, 3, or 4, wherein the acrylic copolymer has a weight average molecular weight of 200,000 to 1,500,000.
  6. 混合モノマーは、更に、ビシクロ環構造と1つのオレフィン性二重結合とを有するモノマー10~60重量%を含有することを特徴とする請求項1、2、3、4又は5記載の光学部材用粘着剤組成物。 6. The optical member according to claim 1, wherein the mixed monomer further contains 10 to 60% by weight of a monomer having a bicyclo ring structure and one olefinic double bond. Adhesive composition.
  7. ビシクロ環構造は、イソボルニル基のビシクロ環構造であることを特徴とする請求項6記載の光学部材用粘着剤組成物。 The pressure-sensitive adhesive composition for an optical member according to claim 6, wherein the bicyclo ring structure is a bicyclo ring structure of an isobornyl group.
  8. オレフィン性二重結合は、(メタ)アクリロイル基のオレフィン性二重結合であることを特徴とする請求項6又は7記載の光学部材用粘着剤組成物。 The pressure-sensitive adhesive composition for an optical member according to claim 6 or 7, wherein the olefinic double bond is an olefinic double bond of a (meth) acryloyl group.
  9. 混合モノマーは、更に、下記一般式(2)で表される構造を有する(メタ)アクリル酸エステルモノマー30~80重量%を含有することを特徴とする請求項1、2、3、4、5、6、7又は8記載の光学部材用粘着剤組成物。
    Figure JPOXMLDOC01-appb-C000003
    一般式(2)中、Rは水素原子又はメチル基を表し、Rは炭素数3~14のアルキル基を表す。Rのアルキル基の水素原子は、シクロアルキル基に置換されていてもよい。
    The mixed monomer further contains 30 to 80% by weight of a (meth) acrylic acid ester monomer having a structure represented by the following general formula (2). , 6, 7 or 8 pressure-sensitive adhesive composition for optical members.
    Figure JPOXMLDOC01-appb-C000003
    In the general formula (2), R 5 represents a hydrogen atom or a methyl group, and R 6 represents an alkyl group having 3 to 14 carbon atoms. The hydrogen atom of the alkyl group of R 6 may be substituted with a cycloalkyl group.
  10. 一般式(2)で表される構造を有する(メタ)アクリル酸エステルモノマーは、2-エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート及びブチル(メタ)アクリレートからなる群より選択される少なくとも1つの(メタ)アクリル酸エステルモノマーを含有することを特徴とする請求項9記載の光学部材用粘着剤組成物。 The (meth) acrylic acid ester monomer having a structure represented by the general formula (2) is at least one selected from the group consisting of 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate and butyl (meth) acrylate. The pressure-sensitive adhesive composition for optical members according to claim 9, comprising a (meth) acrylic acid ester monomer.
  11. 請求項1、2、3、4、5、6、7、8、9又は10記載の光学部材用粘着剤組成物からなる粘着剤層を有することを特徴とする光学部材用粘着テープ。 An adhesive tape for an optical member, comprising an adhesive layer comprising the adhesive composition for an optical member according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
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