WO2012160842A1 - Copolymère d'ester d'acide (méth)acrylique et composition d'agent adhésif le contenant, et procédé de fabrication d'un copolymère d'ester d'acide (méth)acrylique - Google Patents

Copolymère d'ester d'acide (méth)acrylique et composition d'agent adhésif le contenant, et procédé de fabrication d'un copolymère d'ester d'acide (méth)acrylique Download PDF

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WO2012160842A1
WO2012160842A1 PCT/JP2012/052497 JP2012052497W WO2012160842A1 WO 2012160842 A1 WO2012160842 A1 WO 2012160842A1 JP 2012052497 W JP2012052497 W JP 2012052497W WO 2012160842 A1 WO2012160842 A1 WO 2012160842A1
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meth
group
acrylic acid
acid ester
ester copolymer
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PCT/JP2012/052497
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English (en)
Japanese (ja)
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英幸 大塚
淳 高原
太郎 稲田
広一 田口
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電気化学工業株式会社
国立大学法人九州大学
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Publication of WO2012160842A1 publication Critical patent/WO2012160842A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate

Definitions

  • the present invention relates to a (meth) acrylic acid ester copolymer, a pressure-sensitive adhesive composition comprising the same, and a method for producing a (meth) acrylic acid ester copolymer. More specifically, the present invention relates to a (meth) acrylic acid ester copolymer having an alkoxyamine skeleton in the side chain.
  • an acrylic adhesive is a pressure-sensitive adhesive using an acrylic copolymer obtained by crosslinking reaction of an isocyanate compound, an acrylate ester, and a monomer having a hydroxyl group.
  • a polymer is constituted by a strong bond called a covalent bond
  • a special covalent bond dynamic covalent bond
  • an external stimulus such as heat or a catalyst
  • Non-Patent Document 1 discloses a polymer in which a skeleton of “alkoxyamine” is introduced into the main chain of the polymer as a polymer capable of controlling such a structural change.
  • Alkoxyamine is a molecule having a dynamic covalent bond, and has a stable structure at room temperature. However, a part of the bond is reversibly dissociated and added by heating.
  • polyester and polyurethane having an alkoxyamine skeleton introduced into the main chain were synthesized and recombined between the two main chains based on the exchange reaction of the alkoxyamine skeleton, and the polyester and polyurethane were combined. It is described that a polymer was made.
  • isocyanate compounds are extremely reactive with hydroxyl groups or moisture in the air, it is difficult to control the crosslinking reaction with conventional pressure-sensitive adhesives using acrylic and isocyanate copolymers. In some cases, the rest may occur.
  • the main object of the present invention is to provide a novel acrylic copolymer capable of highly controlling the crosslinking reaction.
  • the present invention provides a (meth) acrylic acid ester copolymer having an alkoxyamine skeleton in the side chain.
  • this (meth) acrylic acid ester copolymer is heated, a crosslinked structure is formed between the molecular chains based on the exchange reaction of the alkoxyamine skeleton. Since this crosslinked structure can be reversibly formed and dissociated, the (meth) acrylic acid ester copolymer according to the present invention can be prepared by adjusting the reaction conditions such as temperature and time. The degree of crosslinking can be arbitrarily controlled by changing the crosslinked structure of the polymer.
  • the (meth) acrylic acid ester copolymer according to the present invention can be composed of a structural unit represented by the following general formula (I).
  • R 1 represents a linear or branched alkyl group having 4 to 8 carbon atoms.
  • R 2 to R 4 each represent a hydrogen atom or a methyl group.
  • R 2 to R 4 may be the same or different.
  • R 5 represents a hydrogen atom, an oxygen atom, a hydroxy group, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.
  • the alkyl group and the alkoxy group may have one or more oxygen atom, sulfur atom, carbonyl group, ester group, amide group or imino group in the chain.
  • the copolymerization ratio Y: Z is preferably 0.5: 1 to 2: 1, and the copolymerization ratio X: Y or X: Z is preferably 15: 1 to 25: 1.
  • the present invention also provides a pressure-sensitive adhesive composition comprising the (meth) acrylic acid ester copolymer.
  • the physical properties as a pressure-sensitive adhesive are changed by changing the cross-linked structure formed between the molecular chains of the (meth) acrylate copolymer based on the exchange reaction of the alkoxyamine skeleton by heating. Can be controlled.
  • this invention also provides the manufacturing method of the (meth) acrylic acid ester copolymer which has an alkoxyamine skeleton in a side chain including the process of copolymerizing the acrylate monomer mixture containing the acrylate monomer which has an alkoxyamine skeleton.
  • the step includes a (meth) acrylate monomer having a (meth) acrylate monomer represented by the following general formula (II) and an alkoxyamine skeleton represented by the following general formula (III) and the following general formula (IV). And a step of copolymerizing the monomer.
  • R 1 represents a linear or branched alkyl group having 4 to 8 carbon atoms.
  • R 2 to R 4 each represent a hydrogen atom or a methyl group. R 2 to R 4 may be the same or different.
  • R 5 represents a hydrogen atom, an oxygen atom, a hydroxy group, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 5 to 8 carbon atoms.
  • the cycloalkyl group of is shown.
  • the alkyl group and the alkoxy group may have one or more oxygen atom, sulfur atom, carbonyl group, ester group, amide group or imino group in the chain.
  • the copolymerization ratio of the (meth) acrylate monomer having the alkoxyamine skeleton represented by the general formula (III) and the (meth) acrylate monomer having the alkoxyamine skeleton represented by the formula (IV) is 0.
  • the copolymerization ratio is preferably 15: 1 to 25: 1.
  • 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) as the polymerization initiator in the above step.
  • (meth) acrylic acid means acrylic acid and methacrylic acid.
  • a novel acrylic copolymer capable of highly controlling the crosslinking reaction is provided.
  • FIG. 5 is a drawing-substituting graph showing a differential scanning calorimetry (DSC) thermogram of poly (2EHA-co-ALA1-co-ALA2).
  • FIG. 5 is a drawing-substituting photograph showing photographs of poly (2EHA-co-ALA1-co-ALA2) before heating (a) and after (b).
  • FIG. 6 is a drawing-substituting photograph showing photographs before (a) and after (b) swelling of poly (2EHA-co-ALA1-co-ALA2) after heating.
  • FIG. 3 is a drawing-substituting graph showing the NMR spectrum of the anisole-soluble fraction of poly (2EHA-co-ALA1-co-ALA2) after heating.
  • the (meth) acrylic ester copolymer according to the present invention has an alkoxyamine skeleton having a dynamic covalent bond in a side chain.
  • This (meth) acrylic acid ester copolymer can be produced by copolymerizing an acrylate monomer mixture containing an acrylate monomer having an alkoxyamine skeleton.
  • the (meth) acrylic acid ester copolymer according to the present invention may comprise a structural unit represented by the following general formula (I) as a preferred embodiment.
  • R 1 represents a linear or branched alkyl group having 4 to 8 carbon atoms.
  • R 2 to R 4 each represent a hydrogen atom or a methyl group.
  • R 2 to R 4 may be the same or different.
  • R 5 represents a hydrogen atom, an oxygen atom, a hydroxy group, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.
  • the alkyl group and the alkoxy group may have an oxygen atom, sulfur atom, carbonyl group, ester group, amide group or imino group in the chain.
  • the alkyl group and the alkoxy group may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, or an imino group.
  • the alkoxyamine skeleton is bonded to the main chain of the (meth) acrylic acid ester copolymer via an ester bond, but the bond between the alkoxyamine skeleton and the main chain is For example, a urethane bond, an ether bond, or an amide bond may be used.
  • the (meth) acrylic acid ester copolymer according to the present invention includes a (meth) acrylate monomer represented by the following general formula (II), an alkoxyamine skeleton represented by the following general formula (III) and the following general formula (IV). It can manufacture by copolymerizing the (meth) acrylate monomer which has this.
  • R 1 ⁇ R 5 are the same as R 1 ⁇ R 5 in formula (I).
  • This (meth) acrylic acid ester copolymer corresponds to the case where R 1 is a 2-ethylhexyl group, R 2 to R 4 are hydrogen atoms, and R 5 is a methoxy group in the above formula (I). To do.
  • a (meth) acrylic acid ester copolymer comprising a structural unit represented by the formula (Ia) comprises a 2-ethylhexyl (meth) acrylate monomer and an alkoxyamine skeleton represented by the following formula (IIIa) and the following formula (IVa). It can manufacture by copolymerizing the (meth) acrylate monomer which has.
  • 2-ethylhexyl (meth) acrylate monomer is abbreviated as “2EHA”
  • (meth) acrylate monomers having an alkoxyamine skeleton represented by formula (IIIa) and formula (IVa) are abbreviated as “ALA1” and “ALA2”, respectively.
  • ALA1 alkoxyamine skeleton represented by formula (IIIa) and formula (IVa)
  • Alkoxyamine repeats dissociation and addition of a part of the bond reversibly by heating. Therefore, when the (meth) acrylic acid ester copolymer according to the present invention is heated, a crosslinked structure is formed between the molecular chains based on the exchange reaction of the alkoxyamine skeleton.
  • FIG. 1 shows a cross-linking reaction of a (meth) acrylic acid ester copolymer according to the present invention as an example of a (meth) acrylic acid ester copolymer composed of a structural unit represented by the above general formula (Ia).
  • this cross-linked structure can be reversibly formed and dissociated, by adjusting the reaction conditions such as temperature and time, the cross-linked structure of the (meth) acrylic acid ester copolymer can be changed and the degree of cross-linking can be set arbitrarily. Can be controlled.
  • the crosslinking reaction can be performed under solvent-free conditions (bulk system).
  • the reaction temperature is, for example, 60 to 160 ° C.
  • the reaction time is, for example, 12 to 48 hours, preferably 6 to 24 hours, more preferably 3 to 12 hours, and may be several minutes to several tens of minutes.
  • the solvent-free condition is a condition that substantially does not contain a solvent, and specifically means a condition with a solvent concentration of 1000 ppm or less.
  • the degree of crosslinking of the (meth) acrylic acid ester copolymer by the crosslinking reaction can be arbitrarily controlled by adjusting the introduction amount of the alkoxyamine skeleton (that is, the polymerization rate of ALA1 and ALA2 with respect to 2EHA).
  • the copolymerization ratio of 2EHA and ALA1 (X: Y in general formula (I)) and the copolymerization ratio of 2EHA and ALA2 (X: Z in general formula (I)) are 15: 1 to 25: 1. It is preferably 16: 1 to 20: 1.
  • the copolymerization ratio (Y: Z) of ALA1 and ALA2 is preferably 0.5: 1 to 2: 1. If the copolymerization ratio of 2EHA to ALA1 and ALA2 is too large, the amount of alkoxyamine skeleton that can be crosslinked is reduced, and the copolymer is difficult to crosslink. On the other hand, if the copolymerization ratio is too small, the glass transition temperature of the copolymer is lowered and the adhesiveness is lowered, which is not preferable.
  • the acrylate monomer copolymerized with ALA1 and ALA2 is not limited to 2EHA, but provides a glass transition temperature suitable for the (meth) acrylate copolymer. Therefore, 2EHA is the most preferable.
  • the glass transition temperature of the (meth) acrylic acid ester copolymer according to the present invention is preferably room temperature or lower, for example, 20 ° C. or lower.
  • the glass transition temperature of poly (2-ethylhexyl acrylate) is about -70 ° C.
  • acrylate monomers other than 2EHA include monomers that give polymers having a glass transition temperature of 20 ° C. or lower, such as ethyl acrylate, butyl acrylate, and 2-hydroxyethyl acrylate.
  • the glass transition temperature can also be arbitrarily controlled by adjusting the copolymerization ratio of ALA1 and ALA2 and the acrylate monomer polymerized therewith. From the viewpoint of imparting a suitable glass transition temperature to the (meth) acrylic acid ester copolymer, the copolymerization ratio of the acrylate monomer is preferably in the above-described range.
  • Adhesive composition As described above, the (meth) acrylic acid ester copolymer is heated under a solvent-free condition, and has a crosslinked structure formed between molecular chains based on an exchange reaction of an alkoxyamine skeleton. Can be changed. Therefore, if this (meth) acrylic acid ester copolymer is added to the pressure-sensitive adhesive composition, the physical properties of the pressure-sensitive adhesive composition are controlled by changing the cross-linking structure between the molecular chains based on the exchange reaction of the alkoxyamine skeleton. It becomes possible.
  • the viscosity, adhesive strength, elasticity, heat resistance, solvent resistance, etc. of the pressure-sensitive adhesive composition can be controlled by changing the cross-linking structure between the molecular chains of the (meth) acrylic acid ester copolymer.
  • This pressure-sensitive adhesive composition can be used for various applications, and particularly useful is an adhesive.
  • the pressure-sensitive adhesive composition according to the present invention has a low viscosity because the alkoxyamine skeleton does not form a crosslinked structure before heating, but after heating, the crosslinked structure between molecular chains is based on the exchange reaction of the alkoxyamine skeleton. Agglomerates to form. Therefore, the pressure-sensitive adhesive using the pressure-sensitive adhesive composition according to the present invention can be easily and sufficiently applied and adhered to an uneven surface before heating, and the adhesive remains after heating. It can be easily peeled off from the adherend surface.
  • this adhesive can be used to form a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet used in a manufacturing process of an electronic component.
  • the (meth) acrylic acid ester copolymer according to the present invention can be applied to paints, coating agents, printing inks and the like in addition to the pressure-sensitive adhesive composition.
  • the manufacturing method of the (meth) acrylic acid ester copolymer which concerns on this invention includes the process of copolymerizing the acrylate monomer mixture containing the acrylate monomer which has an alkoxyamine skeleton.
  • the step has a (meth) acrylate monomer represented by the following general formula (II) and an alkoxyamine skeleton represented by the following general formula (III) and the following general formula (IV) (meth). And a step of copolymerizing with an acrylate monomer.
  • R 1 ⁇ R 5 are the same as R 1 ⁇ R 5 in formula (I).
  • the alkoxyamine skeleton is bonded to the main chain of the (meth) acrylic acid ester copolymer via an ester bond.
  • the bond is not limited to an ester bond, and may be, for example, a urethane bond, an ether bond, an amide bond, or the like.
  • each monomer is dissolved in a solvent together with a polymerization initiator and heated as necessary.
  • the radical polymerization reaction proceeds.
  • the solvent for example, toluene, ethyl acetate, methyl ethyl ketone, acetone or the like can be used.
  • the copolymerization of the acrylate monomer mixture can also be performed under solvent-free conditions.
  • the reaction temperature is preferably less than 60 ° C.
  • the reaction time is not particularly limited, but is, for example, within 48 hours.
  • the polymerization initiator it is preferable to use a low-temperature polymerization initiator in order to ensure the thermal stability of the alkoxyamine.
  • the low temperature polymerization initiator is not particularly limited as long as it functions at a temperature lower than the crosslinking reaction temperature (60 to 160 ° C.) based on the exchange reaction of the alkoxyamine skeleton of the (meth) acrylic acid ester copolymer, For example, 2,2′-azobis (2,2′-Azobis (4-methoxy-2.4-dimethylvaleronitrile)), 2,2′-azobisisobutyronitrile, Benzoyl oxide, a redox initiator using a peroxide and a reducing agent in combination, a photopolymerization initiator, and the like can be used.
  • Copolymerization ratio of the (meth) acrylate monomer represented by the above formula (II) and the (meth) acrylate monomer represented by the above formula (III) (X: Y in the general formula (I)) and the above formula (IV)
  • the copolymerization ratio of the (meth) acrylate monomer represented by (X: Z in the general formula (I)) is preferably 15: 1 to 25: 1, and preferably 16: 1 to 20: 1. More preferred.
  • the copolymerization ratio (Y: Z) of the (meth) acrylate monomer represented by the above formula (III) and the (meth) acrylate monomer represented by the above formula (IV) is 0.5: 1 to 2: 1. It is preferable to do.
  • the (meth) acrylate monomer represented by the above formula (III) and the above formula (IV) can be synthesized by a condensation reaction between an acrylic acid chloride and a corresponding alcohol derivative having an alkoxyamine skeleton.
  • Example 1 (1) Synthesis of acrylate monomers (ALA1 and ALA2) having alkoxyamine An acrylate monomer (ALA1) containing an alkoxyamine skeleton was synthesized in one step from the corresponding alkoxyamine. This alkoxyamine has a hydroxyl group and an acryloyl chloride group.
  • the proton NMR spectrum was measured using a Bruker (400 MHz) spectrometer at 25 ° C. with deuterium (CDCl 3 ) using tetramethylsilane (TMS) as an internal standard.
  • a low Tg polymer having an alkoxyamine skeleton is obtained by mixing an acrylate monomer (ALA1 and ALA2) containing 2EHA and two types of alkoxyamines in a molar ratio (2EHA: ALA1: ALA2) 18: 1: 1. Copolymerized and synthesized.
  • the radical copolymerization was carried out in toluene in the presence of the initiator 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) [V-70] for 18 hours at 40 ° C. (conversion of 2EHA) The rate is 93% and the yield is 83%).
  • the structure of the obtained polymer was identified by the NMR spectrum shown in FIG. Since the low temperature initiator V-70 was used for the polymerization, no decomposition of the alkoxyamine was observed.
  • the molar ratio of 2EHA, ALA1, and ALA2 in the obtained polymer could be calculated from the peak area, and the calculated value was in good agreement with the monomer input ratio.
  • FIG. 5 shows a size exclusion chromatography (SEC) chromatogram of poly (2EHA-co-ALA1-co-ALA2).
  • the number average molecular weight (M n ) was 22,000, and the polydispersity index (M w / M n ) was 3.33.
  • DSC differential scanning calorimetry
  • the results are shown in FIG.
  • the Tg of poly (2EHA-co-ALA1-co-ALA2) was estimated to be ⁇ 48 ° C. and was higher than the Tg of P2EHA ( ⁇ 70 ° C.) but belonged to the low Tg polymer class.
  • FIG. 8 (a) shows a photograph of poly (2EHA-co-ALA1-co-ALA2) after heating before being put into anisole.
  • FIG. 8 (b) shows a photograph of poly (2EHA-co-ALA1-co-ALA2) after heating after being placed in anisole for 48 hours.
  • the heated poly (2EHA-co-ALA1-co-ALA2) was not dissolved in anisole but swelled in a gel state. This is a characteristic behavior of the crosslinked polymer, and the progress of the crosslinking reaction could be confirmed.
  • reaction by-product 4-methoxy-1 ((2'-hydroxy-1'-phenylethyl) oxy) -2,2,6,6-tetramethylpiperidine was analyzed.
  • the fraction of anisole dissolved in poly (2EHA-co-ALA1-co-ALA2) after heating was measured by NMR.
  • the (meth) acrylic acid ester copolymer according to the present invention can be used as an adhesive composition, a paint, a coating agent, a printing ink, and the like.
  • the pressure-sensitive adhesive composition according to the present invention can be easily and sufficiently applied even to an uneven surface before heating, and can be easily applied from the surface without any adhesive residue after heating.
  • an adhesive which can be peeled off for example, it can be suitably used for forming an adhesive layer of an adhesive sheet used in the production process of an electronic component.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un copolymère d'ester d'acide (méth)acrylique ayant un squelette d'alcoxyamine dans une chaîne latérale de celui-ci, en tant que nouveau copolymère acrylique dans lequel une réaction de réticulation peut être hautement contrôlée. Le copolymère d'ester d'acide (méth)acrylique comprend une unité structurale représentée par la formule générale (I).
PCT/JP2012/052497 2011-05-23 2012-02-03 Copolymère d'ester d'acide (méth)acrylique et composition d'agent adhésif le contenant, et procédé de fabrication d'un copolymère d'ester d'acide (méth)acrylique WO2012160842A1 (fr)

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FR3030525B1 (fr) * 2014-12-18 2018-05-11 Arkema France Polymerisation radicalaire d'alcoxyamines a basse temperature
FR3030526B1 (fr) * 2014-12-18 2018-06-15 Arkema France Polymerisation radicalaire d'alcoxyamines a basse temperature
JP7314010B2 (ja) 2019-10-02 2023-07-25 ローム株式会社 半導体装置及び電子機器

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JP2008163182A (ja) * 2006-12-28 2008-07-17 Sekisui Fuller Co Ltd 硬化性組成物、並びに硬化性組成物を含む接着剤及びシーリング材
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JP2008163182A (ja) * 2006-12-28 2008-07-17 Sekisui Fuller Co Ltd 硬化性組成物、並びに硬化性組成物を含む接着剤及びシーリング材
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