WO2014148251A1 - (メタ)アクリル系ブロック共重合体およびその製造方法 - Google Patents
(メタ)アクリル系ブロック共重合体およびその製造方法 Download PDFInfo
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- WO2014148251A1 WO2014148251A1 PCT/JP2014/055570 JP2014055570W WO2014148251A1 WO 2014148251 A1 WO2014148251 A1 WO 2014148251A1 JP 2014055570 W JP2014055570 W JP 2014055570W WO 2014148251 A1 WO2014148251 A1 WO 2014148251A1
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- BUJFTKPQXSIZFX-UHFFFAOYSA-N CCC(C)(C)NC Chemical compound CCC(C)(C)NC BUJFTKPQXSIZFX-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- 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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
Definitions
- the present invention relates to a (meth) acrylic block copolymer useful as an active energy ray-curable material. Specifically, the present invention relates to a (meth) acrylic block copolymer that is cured by active energy rays and that the obtained cured product can be softened under wet heat conditions and can be easily separated when discarded. .
- Active energy ray-curable materials that are cured by irradiating with active energy rays such as ultraviolet rays and electron beams are known.
- a (meth) acrylic block copolymer consisting of a methacrylic polymer block and an acrylic polymer block is excellent in tackiness, moldability, weather resistance, etc., making use of these characteristics, adhesives, adhesives, coatings Expansion to applications such as materials, various molding materials, swing tooth fixing materials, denture base materials, and composite resins is expected.
- the object of the present invention is to cure by active energy rays, and when applied to a substrate such as an adhesive or a coating material and then cured by active energy rays, when it is necessary to dispose of it. It is to provide a (meth) acrylic block copolymer capable of easily peeling and separating the cured product and the substrate and a method for producing the same.
- a (meth) acrylic block copolymer consisting of a methacrylic polymer block (A) having at least one curable group and a (meth) acrylic polymer block (B) having no active energy curable group Coalescence hereinafter referred to as “block copolymer (X)”
- block copolymer (X) a methacrylic polymer block having at least one curable group and a (meth) acrylic polymer block (B) having no active energy curable group Coalescence
- step (2) After step (1), adding monomethacrylate and anionic polymerization (2-1); After the step (2-1), a step of adding an monoacrylate and anionic polymerization (2-2); A process for producing the block copolymer (X) according to the above [2];
- the block copolymer (X) and the composition thereof are cured by active energy rays and applied to a substrate such as an adhesive or a coating material and then cured by active energy rays, they are discarded.
- the cured product and the substrate can be easily separated and separated using a wet heat decomposition method or the like.
- the block copolymer (X) has the following general formula (1)
- R 2 and R 3 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group Alkyl groups such as neopentyl group, n-hexyl group, 2-methylpentyl group and 3-methylpentyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group; Can be mentioned. Among these, a methyl group, e
- the hydrocarbon group having 1 to 6 carbon atoms represented by R 2 and R 3 may have a substituent.
- the substituent is not particularly limited as long as it does not inhibit the active energy ray curable property and wet heat decomposability of the active energy ray curable group, and examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, and a t-butoxy group.
- the methacrylic polymer block (A) has the following general formula (1)
- active energy ray-curable monomer a vinyl compound containing an active energy ray-curable group and other ethylenic double bond (hereinafter referred to as “active energy ray-curable monomer”). It is preferable to have a structural unit.
- the content of the structural unit derived from dimethacrylate (2) in the methacrylic polymer block (A) is 5 to 100 mol% with respect to all the structural units forming the methacrylic polymer block (A). It is preferably in the range of 10 to 80 mol%, more preferably in the range of 20 to 70 mol%.
- these dimethacrylates (2) may be used individually by 1 type, or may use 2 or more types together.
- the methacrylic polymer block (A) may have a structural unit derived from monomethacrylate.
- monomethacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, Lauryl methacrylate, dodecyl methacrylate, trimethoxysilylpropyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2-methoxyethyl methacrylate, phenyl methacrylate, naphthyl methacrylate, methacryl Examples include 2- (trimethylsilyloxy) ethyl acid and 3-
- alkyl methacrylates having an alkyl group having 5 or less carbon atoms such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and t-butyl methacrylate are preferable.
- these monomethacrylates may be used individually by 1 type, or may use 2 or more types together.
- the content of the structural unit derived from the monomethacrylate in the methacrylic polymer block (A) is in the range of 0 to 95 mol% with respect to all the structural units forming the methacrylic polymer block (A). Preferably, it is in the range of 20 to 90 mol%, more preferably in the range of 30 to 80 mol%.
- the methacrylic polymer block (A) may have a structural unit derived from a monomer other than dimethacrylate (2) and monomethacrylate.
- the other monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and 2-ethylhexyl acrylate.
- the content of structural units derived from the other monomers in the methacrylic polymer block (A) is preferably 10 mol% or less, and more preferably 5 mol% or less.
- the number average molecular weight of the methacrylic polymer block (A) is not particularly limited, but is 500 to 1,000,000 from the viewpoint of the handleability, fluidity, mechanical properties and the like of the obtained block copolymer (X). It is preferably within the range, and more preferably within the range of 1,000 to 300,000.
- the block copolymer (X) has a (meth) acrylic polymer block (B) having no active energy ray-curable group.
- the active energy ray-curable group is not particularly limited as long as it is a functional group exhibiting polymerizability upon irradiation with active energy rays.
- (meth) acryloyl group, (meth) acryloyloxy group Vinyl group, allyl group, vinyl ether group, 1,3-dienyl group, styryl group and other ethylenic double bonds (particularly represented by the general formula CH 2 ⁇ CHR— (wherein R is an alkyl group or a hydrogen atom))
- a functional group having an ethylenic double bond an epoxy group, an oxetanyl group, a thiol group, a maleimide group, a hydrolyzable silyl group and the like.
- (Meth) acrylic polymer block (B) has a structural unit derived from (meth) acrylic acid ester.
- the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, Isobornyl acrylate, lauryl acrylate, dodecyl acrylate, trimethoxysilylpropyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, 2-methoxyethyl acrylate, phenyl acrylate, acrylic Monoacrylates such as naphthyl acid, 2- (trimethylsilyloxy) ethyl acrylate, 3- (trimethylsilyloxy)
- Examples include monomethacrylates such as n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and dodecyl acrylate.
- these (meth) acrylic acid ester may be used individually by 1 type, or may use 2 or more types together.
- Content of the structural unit derived from the (meth) acrylic acid ester in the (meth) acrylic polymer block (B) is based on all structural units forming the (meth) acrylic polymer block (B). , 90 mol% or more is preferable, and 95 mol% or more is more preferable.
- the (meth) acrylic polymer block (B) may have a structural unit derived from another monomer other than the (meth) acrylic acid ester.
- the other monomers include ⁇ -alkoxy acrylates such as methyl ⁇ -methoxyacrylate and methyl ⁇ -ethoxyacrylate; crotonates such as methyl crotonate and ethyl crotonate; 3-methoxy acrylate 3-alkoxyacrylic acid esters such as N-isopropylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and other acrylamides; N-isopropylmethacrylamide, Nt-butylmethacrylate Examples thereof include amides such as amide, N, N-dimethylmethacrylamide and N, N-diethylmethacrylamide; methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, and
- the content of the structural unit derived from the other monomer in the (meth) acrylic polymer block (B) is preferably 10 mol% or less, more preferably 5 mol% or less. .
- the number average molecular weight of the (meth) acrylic polymer block (B) is not particularly limited. However, from the viewpoint of handling property, fluidity, mechanical properties, etc. of the obtained block copolymer (X), 3,000 to 5 Is preferably in the range of 1,000,000, more preferably in the range of 5,000 to 1,000,000.
- the block copolymer (X) is a block copolymer in which at least one methacrylic polymer block (A) and at least one (meth) acrylic polymer block (B) are bonded to each other.
- the number of combined blocks and the order of bonding are not particularly limited, but from the viewpoint of ease of production of the block copolymer (X), one methacrylic polymer block (A) and one (meth) acrylic heavy polymer.
- the proportion of the methacrylic polymer block (A) having an active energy ray-curable group is 5% by mass or more, the active energy ray curability becomes good, while the proportion of the (meth) acrylic polymer block (B). Is preferably 10% by mass or more, since viscoelasticity is improved.
- the number average molecular weight of the entire block copolymer (X) is not particularly limited, but is 4,000 to 3,000,000 from the viewpoint of handling property, fluidity, mechanical properties, etc. of the block copolymer (X). It is preferably 7,000 to 2,000,000.
- a methacrylic acid ester containing 5 to 100 mol% of dimethacrylate (2) is converted into an organolithium compound, the following general formula (3) Al-O-Ar (3) (In the formula, Ar represents an aromatic ring)
- dimethacrylate (2) a methacryloyl group that is not bonded to the carbon atom to which R 2 and R 3 are bonded is selectively polymerized to bond to the carbon atom to which R 2 and R 3 are bonded. Group polymerization is suppressed and remains in the side chain of the resulting block copolymer (X).
- the dimethacrylate (2) used in the step (1) may be one kind or two or more kinds.
- the methacrylic acid ester used for the step (1) may contain monomethacrylate.
- monomethacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid.
- Lauryl dodecyl methacrylate, trimethoxysilylpropyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2-methoxyethyl methacrylate, phenyl methacrylate, naphthyl methacrylate, methacrylic acid 2 -(Trimethylsilyloxy) ethyl, 3- (trimethylsilyloxy) propyl methacrylate and the like.
- the said monomethacrylate may be used individually by 1 type, or may use 2 or more types together.
- step (1) the molar ratio of dimethacrylate (2) to monomethacrylate in the methacrylic acid ester to be subjected to anionic polymerization is determined by the high polymerization rate and the active energy ray curability of the resulting block copolymer (X). From the viewpoint of wet heat decomposability, it is in the range of 5:95 to 100: 0, preferably in the range of 10:90 to 80:20, more preferably in the range of 20:80 to 70:30. .
- the methacrylic acid ester used in the step (1) may contain a monomer other than dimethacrylate (2) and monomethacrylate.
- the other monomer is not particularly limited as long as it is an anion-polymerizable monomer.
- the content of the other monomer in the methacrylic acid ester used in the step (1) is 10 mol% or less from the viewpoint of active energy ray curability and wet heat decomposability of the obtained block copolymer (X). It is preferable that it is 5 mol% or less.
- this other monomer may be used individually by 1 type, or may use 2 or more types together.
- the monomer used in the step (1) (that is, dimethacrylate (2) and optional monomethacrylate and the other monomers) is preliminarily prepared in an inert gas atmosphere from the viewpoint of allowing the polymerization to proceed smoothly. It is preferable to dry it. In the drying treatment, a dehydrating agent or a drying agent such as calcium hydride, molecular sieves, activated alumina or the like is preferably used.
- the organolithium compound used in step (1) acts as an anionic polymerization initiator.
- the organolithium compound include t-butyl lithium, 2,2-dimethylpropyl lithium, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, ethyl ⁇ -lithioisobutyrate, butyl ⁇ -Lithioisobutyrate, methyl ⁇ -lithioisobutyrate, isopropyl lithium, sec-butyl lithium, 1-methylbutyl lithium, 2-ethylpropyl lithium, 1-methylpentyl lithium, cyclohexyl lithium, diphenylmethyl lithium, ⁇ -methyl Organolithium compounds having 3 to 30 carbon atoms having a chemical structure with a carbon atom as an anion center, such as benzyl lithium, methyl lithium, n-propyl lithium, n-butyl lithium, n-pentyl lithium, and n
- An organolithium compound having 4 to 15 carbon atoms and having a chemical structure having a secondary carbon atom as an anion center is preferred, and sec-butyllithium is particularly preferred.
- these organolithium compounds may be used individually by 1 type, or may use 2 or more types together.
- the amount of the organolithium compound used is 0.0001 to 0 based on the total amount of monomers (that is, dimethacrylate (2) and optional monomethacrylate and other monomers) in the mixture used. It is preferable to use it in a ratio that falls within the range of 3 mole times because the block copolymer (X) can be produced smoothly.
- the tertiary organoaluminum compound used in step (1) depends on the type of monomer used (namely, dimethacrylate (2) and optional monomethacrylate and other monomers), etc.
- a suitable one can be selected, but from the viewpoint of polymerization rate, polymerization initiation efficiency, stability of polymerization terminal anion, etc., the following general formula (3-1) AlR 4 (R 5 ) (R 6 ) (3-1) (Wherein R 4 represents a monovalent saturated hydrocarbon group, monovalent aromatic hydrocarbon group, alkoxy group, aryloxy group or N, N-disubstituted amino group, and R 5 and R 6 are each independently A tertiary organoaluminum compound (hereinafter referred to as an aluminum compound (3-1)) represented by an aryloxy group or an aryleneoxy group bonded to each other, or a compound represented by the following general formula (3-2): AlR 7 (R 8 ) (R 9 ) (3-2) (Wherein R 7 represents an aryl
- Examples of the aryloxy group represented by R 4 , R 5 , R 6 and R 7 include a phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,4-di- t-butylphenoxy group, 2,6-di-t-butylphenoxy group, 2,6-di-t-butyl-4-methylphenoxy group, 2,6-di-t-butyl-4-ethylphenoxy group, Examples include 2,6-diphenylphenoxy group, 1-naphthoxy group, 2-naphthoxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 7-methoxy-2-naphthoxy group and the like.
- Examples of the arylenedioxy group in which R 5 and R 6 are bonded to each other include 2,2′-biphenol, 2,2′-methylenebisphenol, 2,2′-methylenebis (4-methyl-6-t-butylphenol) ), (R)-(+)-1,1′-bi-2-naphthol, (S)-( ⁇ )-1,1′-bi-2-naphthol and the like, hydrogen in two phenolic hydroxyl groups Examples include groups other than atoms.
- the above aryloxy group and aryleneoxy group may have one or more substituents, and examples of the substituent include a methoxy group, an ethoxy group, an isopropoxy group, and a t-butoxy group.
- Alkoxy groups such as halogen atoms such as chlorine and bromine.
- Examples of the monovalent saturated hydrocarbon group represented by R 4 , R 8 and R 9 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t Examples thereof include alkyl groups such as -butyl group, 2-methylbutyl group, 3-methylbutyl group, n-octyl group and 2-ethylhexyl group; cycloalkyl groups such as cyclohexyl group and the like.
- Examples of the aromatic hydrocarbon group represented by R 4 , R 8 and R 9 include an aryl group such as a phenyl group; and an aralkyl group such as a benzyl group.
- Examples of the alkoxy group represented by R 4 , R 8 and R 9 include a methoxy group, an ethoxy group, an isopropoxy group, and a t-butoxy group.
- Examples of the N, N-disubstituted amino group represented by R 4 , R 8 and R 9 include a dialkylamino group such as a dimethylamino group, a diethylamino group and a diisopropylamino group; a bis (trimethylsilyl) amino group, and the like.
- the functional groups represented by R 4 , R 8 and R 9 are, for example, alkoxy groups such as methoxy group, ethoxy group, isopropoxy group and t-butoxy group; and substituents such as halogen atoms such as chlorine and bromine. You may have.
- Examples of the aluminum compound (3-1) include methyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum, ethyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum, ethyl bis (2,6-di-t-butylphenoxy) aluminum, ethyl [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, isobutylbis (2,6-di-t-butyl- 4-methylphenoxy) aluminum, isobutylbis (2,6-di-t-butylphenoxy) aluminum, isobutyl [2,2′-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, n-octylbis ( 2,6-di-tert-butyl-4-methylphenoxy) aluminum, n-octylbis (2, -Di-t-butylphenoxy) aluminum, n-octyl [2,
- isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6 -Di-t-butylphenoxy) aluminum, isobutyl [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum and the like are preferable.
- Examples of the aluminum compound (3-2) include diethyl (2,6-di-t-butyl-4-methylphenoxy) aluminum, diethyl (2,6-di-t-butylphenoxy) aluminum, diisobutyl (2,6 -Di-t-butyl-4-methylphenoxy) aluminum, diisobutyl (2,6-di-t-butylphenoxy) aluminum, di-n-octyl (2,6-di-t-butyl-4-methylphenoxy) aluminum And di-n-octyl (2,6-di-t-butylphenoxy) aluminum.
- These tertiary organoaluminum compounds may be used alone or in combination of two or more.
- the amount of the tertiary organoaluminum compound used can be appropriately selected in accordance with the type of solvent, other various polymerization conditions, etc., but is usually 1 with respect to 1 mol of the organolithium compound from the viewpoint of the polymerization rate. It is preferably used in the range of 0.0 to 10.0 mol, more preferably in the range of 1.1 to 5.0 mol, and still more preferably in the range of 1.2 to 4.0 mol. When the amount of the tertiary organoaluminum compound used exceeds 10.0 mol with respect to 1 mol of the organolithium compound, it tends to be economically disadvantageous. It tends to decrease.
- the Lewis base used in step (1) is selected from the group consisting of ethers and tertiary polyamines.
- the ether can be appropriately selected from compounds having an ether bond in the molecule, but from the viewpoint of polymerization initiation efficiency and stability of the polymerization terminal anion, a cyclic ether having two or more ether bonds in the molecule and one or more ethers Acyclic ethers having an ether bond in the molecule are preferred.
- Examples of the cyclic ether having two or more ether bonds in the molecule include crown ethers such as 12-crown-4, 15-crown-5, and 18-crown-6.
- acyclic ether having one or more ether bonds in the molecule examples include acyclic monoethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, and anisole; 1,2-dimethoxyethane, 1,2-diethyl Ethoxyethane, 1,2-diisopropoxyethane, 1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-diisopropoxy Propane, 1,2-dibutoxypropane, 1,2-diphenoxypropane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3-dibutoxypropane, 1,3-diphenoxypropane, 1,4-dimethoxybutane, 1,4-diethoxybutane
- Acyclic diethers such as 1,4-di
- the tertiary polyamine that can be used as the Lewis base means a compound having two or more tertiary amine structures in the molecule.
- the tertiary polyamine include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N, N ′, N ′′, N ′′ -pentamethyl.
- Linear polyamines such as diethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine, tris [2- (dimethylamino) ethyl] amine; 1,3,5-trimethylhexahydro-1, 3,5-triazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16 -Non-aromatic heterocyclic compounds such as hexaazacyclooctadecane; aromatic heterocyclic compounds such as 2,2'-bipyridyl, 2,2 ': 6', 2 "-terpyridine and the like.
- a compound having one or more ether bonds and one or more tertiary amine structures in the molecule may be used as the Lewis base.
- examples of such a compound include tris [2- (2-methoxyethoxy) ethyl] amine.
- these Lewis bases may be used individually by 1 type, or may use 2 or more types together.
- the amount of the Lewis base used is preferably in the range of 0.3 to 5.0 moles with respect to 1 mole of the organolithium compound from the viewpoints of polymerization initiation efficiency, stability of the polymerization terminal anion, and the like.
- the range is more preferably in the range of -3.0 mol, and still more preferably in the range of 1.0-2.0 mol.
- the amount of the Lewis base used exceeds 5.0 mol with respect to 1 mol of the organolithium compound, it tends to be disadvantageous in terms of economy, and when it is less than 0.3 mol, the anion polymerization initiation efficiency tends to decrease. .
- the amount of the Lewis base used is preferably in the range of 0.2 to 1.2 mol, and preferably in the range of 0.3 to 1.0 mol, with respect to 1 mol of the tertiary organoaluminum compound. More preferred.
- Step (1) is preferably carried out in the presence of an organic solvent from the viewpoint of controlling the temperature of anionic polymerization and making the system uniform to smoothly proceed with anionic polymerization.
- Organic solvents include hydrocarbons such as toluene, xylene, cyclohexane, and methylcyclohexane from the viewpoints of safety, separability from water in washing the reaction mixture after anionic polymerization, and ease of recovery and reuse; chloroform Halogenated hydrocarbons such as methylene chloride and carbon tetrachloride are preferred.
- These organic solvents may be used alone or in combination of two or more.
- the amount of organic solvent used is as follows: monomer used (ie, dimethacrylate (2) and optional monomethacrylate and other monomers), organolithium compound used, tertiary organoaluminum compound, Lewis base
- monomer used ie, dimethacrylate (2) and optional monomethacrylate and other monomers
- organolithium compound used ie, dimethacrylate (2) and optional monomethacrylate and other monomers
- tertiary organoaluminum compound tertiary organoaluminum compound
- Lewis base The amount of the monomer used can be adjusted to 100 parts by weight from the viewpoint of smooth progress of anionic polymerization, separation and acquisition of the generated block copolymer (X), waste liquid treatment, and the like. On the other hand, it is preferably in the range of 150 to 10000 parts by mass, more preferably in the range of 200 to 3000 parts by mass.
- the anionic polymerization is preferably carried out at ⁇ 100 to 50 ° C., and particularly preferably carried out at ⁇ 30 to 25 ° C. from the viewpoint of polymerization control and productivity.
- the temperature is lower than ⁇ 100 ° C., the polymerization rate decreases and the productivity tends to decrease.
- the temperature is higher than 50 ° C., it is difficult to suppress polymerization of the (meth) acryloyl group bonded to the carbon atom to which R 2 and R 3 of dimethacrylate (2) are bonded, and the resulting block copolymer (X ) Active energy ray curability and wet heat decomposability tend to decrease.
- the anionic polymerization is preferably performed in an atmosphere of an inert gas such as nitrogen, argon or helium. Furthermore, it is preferable to carry out it under sufficient stirring conditions so that the reaction system of anionic polymerization becomes uniform.
- step (1) the method of adding the organolithium compound, the tertiary organoaluminum compound, the Lewis base and the methacrylic acid ester to the reaction system of the anionic polymerization is not particularly limited.
- the Lewis base is preferably added so as to come into contact with the tertiary organoaluminum compound before contact with the organolithium compound.
- the tertiary organoaluminum compound may be added to the anionic polymerization reaction system prior to the methacrylic acid ester, or may be added simultaneously.
- the tertiary organoaluminum compound When the tertiary organoaluminum compound is added to the anionic polymerization reaction system simultaneously with the methacrylic acid ester, the tertiary organoaluminum compound may be added after separately mixing with the methacrylic acid ester. Moreover, you may make another additive exist in the reaction system of anionic polymerization as needed. Examples of the other additives include inorganic salts such as lithium chloride; metal alkoxides such as lithium methoxyethoxy ethoxide and potassium t-butoxide; tetraethylammonium chloride and tetraethylphosphonium bromide.
- inorganic salts such as lithium chloride
- metal alkoxides such as lithium methoxyethoxy ethoxide and potassium t-butoxide
- tetraethylammonium chloride tetraethylphosphonium bromide.
- the method for producing the block copolymer (X) in the present invention further includes a step (2) of adding mono (meth) acrylate and anionic polymerization after the step (1).
- Mono (meth) acrylate used in step (2) includes methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, acrylic acid 2-ethylhexyl, isobornyl acrylate, lauryl acrylate, dodecyl acrylate, trimethoxysilylpropyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, 2-methoxyethyl acrylate, acrylic Monoacrylates such as phenyl acrylate, naphthyl acrylate, 2- (trimethylsilyloxy) ethyl acrylate, 3- (trimethylsilyloxy) propyl acrylate; methyl methacrylate, ethyl methacrylate, n-
- Alkyl monoacrylate and 2-ethylhexyl methacrylate having a prime number of 4 or more alkyl groups lauryl methacrylate, alkyl monomethacrylate is preferred to have an alkyl group having 6 or more carbon atoms such as dodecyl methacrylate.
- These mono (meth) acrylates may be used alone or in combination of two or more.
- the other monomer is not particularly limited as long as it is an anion-polymerizable monomer, and examples thereof include ⁇ -alkoxy acrylate esters such as methyl ⁇ -methoxyacrylate and methyl ⁇ -ethoxyacrylate; Crotonic acid esters such as methyl acid and ethyl crotonic acid; 3-alkoxy acrylic acid esters such as 3-methoxyacrylic acid ester; N-isopropylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N, N- Acrylamide compounds such as diethylacrylamide; N-isopropylmethacrylamide, Nt-butylmethacrylamide, N, N-dimethylmethacrylamide, methacrylamide compounds such as N, N-diethylmethacrylamide; methyl vinyl ketone, ethyl
- this other monomer is 10 mol% or less of all the monomers used at a process (2), and it is more preferable that it is 5 mol% or less.
- this other monomer may be used individually by 1 type, or may use 2 or more types together.
- the monomer used in the step (2) (that is, the mono (meth) acrylate and the other monomer as an optional component) is dried in advance under an inert gas atmosphere from the viewpoint of smoothly proceeding the polymerization. It is preferable to keep it.
- a dehydrating agent or a drying agent such as calcium hydride, molecular sieves, activated alumina or the like is preferably used.
- a tertiary organoaluminum compound, a Lewis base, and an organic solvent are used as a reaction system for anionic polymerization. It may be added.
- the tertiary organoaluminum compound, Lewis base, and organic solvent include tertiary organoaluminum compounds, Lewis bases, and organic solvents that can be used in the above-described step (1).
- the amount of these tertiary organoaluminum compound, Lewis base and organic solvent used can be suitably selected according to the type of solvent and other various polymerization conditions.
- step (2) a monomer that may be used in step (2) (that is, mono (meth) acrylate and other optional monomers), a tertiary organoaluminum compound, a Lewis base, and an organic solvent
- the method for adding to the reaction system of anionic polymerization is not particularly limited. Moreover, you may make another additive exist in the reaction system of anionic polymerization as needed. Examples of the other additives include inorganic salts such as lithium chloride; metal alkoxides such as lithium methoxyethoxy ethoxide and potassium t-butoxide; tetraethylammonium chloride and tetraethylphosphonium bromide.
- step (2) the anionic polymerization is preferably performed at ⁇ 100 to 50 ° C., particularly preferably ⁇ 30 to 25 ° C. from the viewpoint of polymerization control and productivity.
- step (2) from the viewpoint of improving the stability of the polymerization terminal anion, after the step (1), monomethacrylate is added and anion polymerization is performed (2-1); After the step (2-1), a step of adding an monoacrylate and anionic polymerization (2-2); Are preferably included.
- the above-mentioned monomethacrylate can be used.
- the monomethacrylate used in the step (2-1) may be one kind or two or more kinds.
- Examples of the monoacrylate used in step (2-2) include the monoacrylates described above.
- the monoacrylate used in the step (2-2) may be one type or two or more types.
- the method for producing the block copolymer (X) in the present invention comprises a step of anionic polymerization by adding a methacrylic acid ester containing dimethacrylate (2) after the step (2) or the step (2-2). (3) may further be included.
- dimethacrylate (2) may be used alone or in combination of two or more.
- the dimethacrylate (2) that may be used in the step (3) may be the same as or different from the step (1).
- the methacrylic acid ester used in step (3) may contain monomethacrylate together with dimethacrylate (2).
- monomethacrylate examples include monomethacrylate that may be used in the above-described step (1).
- the monomethacrylate used at a process (3) may be only 1 type, or 2 or more types. Further, the same type of monomethacrylate as in step (1) or step (2) may be used, or other types of monomethacrylate may be used.
- the molar ratio of dimethacrylate (2) to monomethacrylate in the methacrylic acid ester used in step (3) is preferably in the range of 5:95 to 100: 0, and in the range of 10:90 to 80:20. More preferably, it is in the range of 20:80 to 70:30.
- the methacrylic acid ester used in step (3) may further use a monomer other than dimethacrylate (2) and monomethacrylate.
- the other monomer include the same monomers as those exemplified in the step (1).
- the content of the other monomer in the methacrylic acid ester used in the step (3) is 10 mol% or less from the viewpoint of the active energy ray curability and the wet heat decomposability of the resulting block copolymer (X). Preferably, it is 5 mol% or less.
- the dimethacrylate (2) used in the step (3), the optional monomethacrylate, and the other monomers may be previously dried in an inert gas atmosphere from the viewpoint of smooth polymerization. preferable.
- a tertiary organoaluminum compound, a Lewis base and an organic solvent may be added to the reaction system for anionic polymerization.
- the tertiary organoaluminum compound, Lewis base, and organic solvent include tertiary organoaluminum compounds, Lewis bases, and organic solvents that can be used in the above-described step (1).
- the amount of these tertiary organoaluminum compound, Lewis base and organic solvent used can be suitably selected according to the type of solvent and other various polymerization conditions.
- a monomer that may be used in step (3) ie, dimethacrylate (2) and optional monomethacrylate and other monomers
- tertiary organoaluminum compound Lewis
- the method for adding the base and the organic solvent to the anionic polymerization reaction system is not particularly limited. Moreover, you may make another additive exist in the reaction system of anionic polymerization as needed. Examples of the other additives include inorganic salts such as lithium chloride; metal alkoxides such as lithium methoxyethoxy ethoxide and potassium t-butoxide; tetraethylammonium chloride and tetraethylphosphonium bromide.
- step (3) the anionic polymerization is preferably performed at ⁇ 100 to 50 ° C., particularly preferably ⁇ 30 to 25 ° C. from the viewpoint of polymerization control and productivity.
- anionic polymerization can be stopped by adding a polymerization terminator such as methanol; a methanol solution of acetic acid or hydrochloric acid; a protic compound such as an aqueous solution of acetic acid or hydrochloric acid to the reaction mixture.
- a polymerization terminator such as methanol; a methanol solution of acetic acid or hydrochloric acid; a protic compound such as an aqueous solution of acetic acid or hydrochloric acid
- the amount of the polymerization terminator used is usually preferably in the range of 1 to 100 mol per 1 mol of the organic lithium compound used.
- a known method can be employed as a method for separating and obtaining the block copolymer (X) from the reaction mixture after termination of anionic polymerization. For example, a method of pouring the reaction mixture into a poor solvent of the block copolymer (X) to precipitate the block copolymer (X), distilling off the organic solvent from the reaction mixture and removing the block copolymer (X) The acquisition method etc. are mentioned.
- the metal component derived from the organolithium compound and the tertiary organoaluminum compound remains in the separated and obtained block copolymer (X), the physical properties of the block copolymer (X) are deteriorated and the transparency is increased. Defects may occur. Therefore, it is preferable to remove the metal component derived from the organolithium compound and the tertiary organoaluminum compound after the anionic polymerization is stopped.
- a method for removing the metal component it is effective to subject the block copolymer (X) to a washing treatment using an acidic aqueous solution, an adsorption treatment using an adsorbent such as an ion exchange resin, celite, or activated carbon. is there.
- acidic aqueous solution hydrochloric acid, sulfuric acid aqueous solution, nitric acid aqueous solution, acetic acid aqueous solution, propionic acid aqueous solution, citric acid aqueous solution etc. can be used, for example.
- a block copolymer (X) having a narrow molecular weight distribution is usually obtained, and a block copolymer (X) having a molecular weight distribution (Mw / Mn) of 1.5 or less is produced. Can do.
- the block copolymer (X) of the present invention comprises a photopolymerization initiator, a compound other than the block copolymer (X) exhibiting polymerizability upon irradiation with active energy rays (hereinafter referred to as a reactive diluent), active energy.
- a reactive diluent active energy.
- the active energy ray-curable composition of the present invention can be obtained by blending with an organic compound that is stable to rays (hereinafter referred to as an inert diluent) and the like.
- photopolymerization initiator examples include acetophenones (for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl- Propan-1-one, etc.), benzophenones (eg, benzophenone, benzoylbenzoic acid, hydroxybenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, acrylated benzophenone, etc.), mihiraketones (eg, mihiraketone, etc.)
- carbonyl compounds such as benzoin, benzoin methyl ether, benzoin isopropyl ether, etc., tetramethylthiuram monosulfide, thioxanthones (eg, thioxanthone, 2-chlorothioxanthone, etc.)
- acetophenones for example, 1-hydroxycyclohexyl phen
- a sensitizer may be used as necessary.
- the sensitizer include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiouric acid, triethylamine, diethylaminoethyl methacrylate and the like. Triethylamine and diethylaminoethyl methacrylate are preferred.
- the mass ratio of the photopolymerization initiator to the sensitizer is preferably 10:90 to 90:10, and more preferably 20:80 to 80:20.
- the amount of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass with respect to 100 parts by mass of the block copolymer (X).
- the amount is less than 0.01 parts by mass, the curability of the active energy ray-curable composition tends to be insufficient, and when the amount exceeds 10 parts by mass, the curing rate of the active energy ray-curable composition is too high, and thus obtained.
- the cured product has a low molecular weight and tends to lack heat resistance.
- Examples of the reactive diluent include compounds that can be cured by irradiation with active energy rays, and specifically include styrene, indene, p-methylstyrene, ⁇ -methylstyrene, p-methoxystyrene, p-tert-butoxy.
- Styrene derivatives such as styrene, p-chloromethylstyrene, p-acetoxystyrene, divinylbenzene; fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate; ) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid t -Butyl butyl, (meth) acrylic acid pentyl, (meth) acrylic Isoamyl, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth
- epoxy acrylate resins such as bisphenol A type epoxy acrylate resins, phenol novolac type epoxy acrylate resins, cresol novolac type epoxy acrylate resins, COOH group-modified epoxy acrylate resins, polyols (polytetramethylene glycol, Polyester diol of ethylene glycol and adipic acid, ⁇ -caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, Urethane resin obtained from carbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanate (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc.) A urethane acrylate resin obtained by react
- the mass ratio of the block copolymer (X) to the reactive diluent is in the range of 10:90 to 90:10 from the viewpoint of the viscosity of the resulting active energy ray-curable composition and the mechanical properties of the cured product. It is preferably in the range of 20:80 to 80:20.
- Examples of the purpose of containing the inert diluent include adjustment of the viscosity of the active energy ray-curable composition and the mechanical strength of a cured product obtained by curing the active energy ray-curable composition.
- Inert diluents suitable for this purpose include compounds that do not have an active energy ray-curable group. Specific examples include dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate.
- Non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; diethylene glycol dibenzoate Polyalkylene glycol esters such as triethylene glycol dibenzoate and pentaerythritol ester; phosphate esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; Polystyrenes such as ⁇ -methylstyrene; polybutadiene; polybutene; polyisobutylene; butadiene-acrylonitrile copolymer; polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils Polyether polyols such as polyethylene glycol
- the amount of these inert diluents used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and still more preferably 20 to 120 parts by weight with respect to 100 parts by weight of the block copolymer (X). 100 parts by mass.
- the amount to 5 parts by mass or more effects such as physical property adjustment and property adjustment become remarkable, and by setting the amount to 150 parts by mass or less, a cured product obtained by curing the active energy ray-curable composition tends to have excellent mechanical strength. .
- an inert diluent which is a polymer having a number average molecular weight of 400 to 15,000 (preferably 800 to 10,000, more preferably 1,000 to 8,000).
- an inactive polymer may or may not have a functional group (such as a hydroxyl group, a carboxyl group, or a halogen group) other than the active energy ray-curable group.
- the molecular weight of the inert polymer is 400 or more, the inert polymer does not flow out from the cured product of the active energy ray-curable composition with time, and the initial physical properties can be maintained for a long time.
- an active energy ray-curable composition to improve because the molecular weight of an inactive polymer is 15,000 or less.
- the molecular weight distribution of the inert polymer is not particularly limited, but is usually less than 1.8, preferably 1.7 or less, more preferably 1.6 or less, further preferably 1.5 or less, and particularly preferably 1.4 or less. Preferably, 1.3 or less is the most preferable.
- inert polymers those that are compatible with the block copolymer (X) are preferable.
- vinyl polymers are more preferable in terms of compatibility, weather resistance, and heat resistance, and (meth) acrylic heavy polymers.
- a coalescence is further preferred, and an acrylic polymer is particularly preferred.
- examples of such an acrylic polymer include n-butyl polyacrylate and 2-ethylhexyl polyacrylate.
- Examples of the method for synthesizing the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers.
- the latter acrylic plasticizer does not use a solvent or a chain transfer agent and is a high-temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-331522, USP 5010166). It is more preferable for the purpose of the present invention. Examples thereof include, but are not limited to, Toagosei UP series and the like (see the Industrial Materials October 1999 issue).
- Another synthetic method may include a living radical polymerization method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.
- inert diluent is to impart tackiness to a cured product obtained by curing the active energy ray-curable composition.
- suitable inert diluents for this purpose include, for example, chroman indene resin, phenol resin, pt-butylphenol acetylene resin, phenol formaldehyde resin, polyterpene resin, xyleneformaldehyde resin, synthetic polyterpene resin, aromatic Hydrocarbon resins, aliphatic cyclic hydrocarbon resins, oligomers of monoolefins and diolefins, hydrocarbon resins, hydrogenated hydrocarbon resins, polybutenes, polyhydric alcohol esters of rosin, hydrogenated rosin, hydrogenated wood rosin, hydrogenated Examples thereof include esters of rosin and monoalcohols or polyhydric alcohols, and terpine tackifying resins.
- tackifying resins are terpene resins, synthetic terpene resins, aromatic modified polyterpene resins, aliphatic saturated petroleum resins, rosin esters, disproportionated rosin esters, hydrogenated rosin esters, aliphatic petroleum resins (C5 Aliphatic aliphatic petroleum resins, C5 / C9 aliphatic petroleum resins, etc.) and modified aliphatic petroleum resins.
- the active energy ray-curable composition of the present invention contains, as an optional component, various conventionally known additives such as softeners, fillers, stabilizers, pigments, and dyes within a range that does not significantly impair the curability thereof. But you can. These additives may be organic compounds (inert diluents) or inorganic compounds.
- the active energy ray used for curing the active energy ray-curable composition of the present invention includes deep ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays and other electromagnetic waves, X rays, ⁇ rays and other electromagnetic waves, electron beams, Although proton beam, neutron beam, and the like can be used, curing by ultraviolet ray or electron beam irradiation is preferable, and curing by ultraviolet ray irradiation is more preferable from the viewpoint of curing speed, availability of irradiation apparatus, price, and the like.
- active energy rays can be irradiated using a known apparatus.
- the acceleration voltage is suitably 0.1 to 10 MeV
- the irradiation dose is suitably 1 to 500 kGy.
- a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an LED, or the like that emits light in a wavelength range of 150 to 450 nm can be used.
- Integrated light quantity of the active energy ray is usually in the range of 10 ⁇ 20000mJ / cm 2, preferably in the range of 30 ⁇ 5000mJ / cm 2. When it is less than 10 mJ / cm 2, the curability of the active energy ray-curable composition becomes insufficient, and when it is more than 20000 mJ / cm 2 , the active energy ray-curable composition may be deteriorated.
- the relative humidity when irradiating the active energy ray-curable composition of the present invention with active energy rays is preferably 30% or less from the viewpoint of suppressing the decomposition of the active energy ray-curable composition. % Or less is more preferable.
- the active energy ray-curable composition of the present invention can be further heated during the active energy ray irradiation or after irradiation to accelerate the curing as necessary.
- a heating temperature is preferably in the range of 40 to 130 ° C, more preferably in the range of 50 to 100 ° C.
- the active energy ray-curable composition of the present invention can be easily applied to a cured product and a substrate when it needs to be disposed of after being applied to a substrate such as an adhesive or a coating material and cured. Can be separated and separated.
- the peeling method the wet heat decomposition method is preferable from the viewpoint of workability and economy.
- the temperature at which the wet pyrolysis method is performed (wet pyrolysis temperature) is preferably 100 to 250 ° C, and more preferably 130 to 220 ° C.
- the relative humidity (humid heat decomposition relative humidity) at which the wet pyrolysis method is performed is preferably 10 to 100%, and more preferably 30 to 100%.
- the time required for the wet pyrolysis method (wet pyrolysis time) is preferably 1 minute to 24 hours, more preferably 1 minute to 5 hours, and further preferably 1 minute to 2 hours.
- Applications of the active energy ray-curable composition of the present invention include curable resins and adhesives used in fields such as automobiles, home appliances, architecture, civil engineering, sports, displays, optical recording equipment, optical equipment, semiconductors, batteries, and printing.
- Adhesive tape, film, sheet, mat, sealing material, sealing material, coating material, potting material, ink, printing plate material, anti-vibration material, foam, heat dissipation material, prepreg, gasket, packing, etc.
- Waterproof packing, heater packing, electrode packing, safety valve diaphragm, hoses for sake cans, waterproof packing, solenoid valves, waterproof packing for steam microwave ovens and jar rice cookers, water tank packing, water absorption valve, water receiving packing, Connection hose, belt, insulation heater packing, steam outlet seal, etc., oil packing for combustion equipment, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil Loudspeaker gasket, oil supply pipe, diaphragm valve, air supply pipe, etc.
- Ejji turntable seat, belts, pulleys, etc.
- Structural gaskets zipper gaskets
- air membrane roofing materials waterproof materials, fixed sealing materials, anti-vibration materials, soundproof materials, setting blocks, sliding materials, etc.
- Sports floors all-weather pavement materials, gymnasium floors, etc.
- sports shoe components shoe sole materials, midsole materials, etc.
- ball balls golf balls, etc.
- Architectural applications such as roofs, floors, shutters, curtain rails, floors, piping ducts, deck plates, curtain walls, stairs, doors, vibration isolator, structural damping materials
- Structural materials rubber expansion joints, bearings, waterproof plates, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc.
- construction sub-materials rubber molds, rubber packers, rubber skirts, etc.
- Sponge mats mortar hoses, mortar strainers, etc.
- construction auxiliary materials rubber sheets, air hoses, etc.
- safety measures rubber buoys, wave-dissipating materials, etc.
- environmental protection products oil fences, silt fences, antifouling materials, marine) Hose, draging hose, oil skimmer, etc.
- the raw materials were dried and purified by a conventional method and degassed with nitrogen, and the transfer and supply were performed in a nitrogen atmosphere.
- Example 1 100 ml of toluene was added to a 300 ml flask whose interior was dried and purged with nitrogen, and 1,1,4,7,10,10-hexamethyltriethylenetetramine was added as a Lewis base while stirring the solution in the flask. After sequentially adding 12.7 ml of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as a tertiary organoaluminum compound, .78 ml (2.86 mmol). , Cooled to -20 ° C.
- step (1) To this was added 2.00 ml of a 1.30 mol / L cyclohexane solution of sec-butyllithium as the organolithium compound, and 2.47 ml of 1,1-dimethylpropane-1,3-diol dimethacrylate as dimethacrylate (2) (10. 4 mmol) and 3.58 ml of a mixture of 1.11 ml (10.4 mmol) of methyl methacrylate as monomethacrylate were added all at once to initiate anionic polymerization. Ten minutes after the completion of the addition of the mixture, the polymerization reaction solution changed from the original yellow color to colorless. After stirring for another 10 minutes, the reaction solution obtained in step (1) was sampled.
- the obtained solution was poured into 1 liter of methanol, and the produced block copolymer (X) was precipitated and collected.
- the consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step (1) was 100%.
- Mn of the polymer obtained at the process (1) was 1,500, and Mw / Mn was 1.13.
- the initiator efficiency (F1) in the step (1) was 91%.
- the consumption rate of methyl methacrylate and n-butyl acrylate in step (2) was 100%.
- Mn of the obtained block copolymer (X) was 24,700, and Mw / Mn was 1.21.
- the block efficiency (F2) from step (1) to step (2) was 65%. The results are shown in Table 1.
- Example 2 After obtaining the reaction solution of step (1) in the same manner as in Example 1, subsequently, after 20 minutes from the start of polymerization in step (1), 37.4 ml (260 mmol) of n-butyl acrylate as monoacrylate was added to -20. It was added to the reaction solution at a rate of 1 ml / min at 0 ° C. Immediately after the completion of the addition of n-butyl acrylate, the reaction solution in step (2) was sampled. Subsequently, 10.0 ml of methanol was added at ⁇ 20 ° C. while stirring the reaction solution obtained in the step (2) to stop anionic polymerization.
- the obtained solution was poured into 1 liter of methanol, and the produced block copolymer (X) was precipitated and collected.
- the consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step (1) was 100%.
- Mn of the polymer obtained at the process (1) was 1,520, and Mw / Mn was 1.15.
- the initiator efficiency (F1) in the step (1) was 90%.
- the consumption rate of n-butyl acrylate in step (2) was 100%.
- Mn of the obtained block copolymer (X) was 41,700, and Mw / Mn was 1.20.
- the block efficiency (F2) from step (1) to step (2) was 34%. The results are shown in Table 1.
- step (1) 2.61 ml (10.4 mmol) of 1,1-dimethylbutane-1,4-diol dimethacrylate as dimethacrylate (2) and 1.11 ml (10.4 mmol) of methyl methacrylate as monomethacrylate Polymerization was carried out in the same manner as in Example 1, except that 3.72 ml of the mixture was added.
- the consumption rate of 1,1-dimethylbutane-1,4-diol dimethacrylate and methyl methacrylate in step (1) was 100%.
- Mn of the polymer obtained at the process (1) was 1,420, and Mw / Mn was 1.14.
- the initiator efficiency (F1) in the step (1) was 99%.
- the consumption rate of methyl methacrylate and n-butyl acrylate in step (2) was 100%. Moreover, Mn of the obtained block copolymer (X) was 16,900, and Mw / Mn was 1.15. Furthermore, the block efficiency (F2) from the step (1) to the step (2) was 85%. The results are shown in Table 1.
- step (1) 2.61 ml (10.4 mmol) of 1,1-dimethylbutane-1,4-diol dimethacrylate as dimethacrylate (2) and 1.11 ml (10.4 mmol) of methyl methacrylate as monomethacrylate Polymerization was carried out in the same manner as in Example 2, except that 3.72 ml of the mixture was added.
- the consumption rate of 1,1-dimethylbutane-1,4-diol dimethacrylate and methyl methacrylate in step (1) was 100%.
- Mn of the polymer obtained at the process (1) was 1,580, and Mw / Mn was 1.16.
- the initiator efficiency (F1) in the step (1) was 90%.
- step (2) The consumption rate of n-butyl acrylate in step (2) was 100%. Moreover, Mn of the obtained block copolymer (X) was 29,200 and Mw / Mn was 1.27. Furthermore, the block efficiency (F2) from step (1) to step (2) was 50%. The results are shown in Table 1.
- Example 1 and Example 3 include a step (2-1) of adding monomethacrylate after step (1) and anionic polymerization; and a step of anionic polymerization by adding monoacrylate after step (2-1) ( 2-2);
- the block efficiency (F2) from Step (1) to Step (2) is high. This shows that the stability of the polymerization terminal anion during the polymerization is improved.
- step (2) after step (1), monomethacrylate is added, and anionic polymerization is performed (2-1) and after step (2-1).
- step (2-2) of adding monoacrylate and anionic polymerization is shown to be preferable.
- Example 5 After obtaining the reaction solution of step (2) in the same manner as in Example 1, the dimethacrylate (2) was added at ⁇ 20 ° C. immediately after the addition of n-butyl acrylate while stirring the reaction solution of step (2). 3.58 ml of a mixture of 1,1-dimethylpropane-1,3-diol dimethacrylate 2.47 ml (10.4 mmol) as a monomethacrylate and 1.11 ml (10.4 mmol) methyl methacrylate as a monomethacrylate were added all at once. Thereafter, the temperature was raised to 0 ° C. at a rate of 5 ° C./min. 120 minutes after the addition of the mixture, the reaction solution in step (3) was sampled.
- step (3) 10.0 ml of methanol was added while stirring the reaction solution obtained in step (3) to stop anionic polymerization.
- the obtained solution was poured into 1 liter of methanol, and the produced block copolymer (X) was precipitated and collected.
- the consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step (3) was 100%.
- Mn of the obtained block copolymer (X) was 26,300, and Mw / Mn was 1.22.
- the obtained block copolymer (X) was dissolved in dicyclopentenyloxyethyl methacrylate (FA-512M, manufactured by Hitachi Chemical Co., Ltd.) as a reactive diluent (photopolymerizable monomer) to obtain a 70% by mass solution. . 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator in a solution state was blended with the obtained solution to obtain an active energy ray-curable composition.
- F-512M dicyclopentenyloxyethyl methacrylate
- UV curability test On the release surface of the release PET film (K1504, manufactured by Toyobo Co., Ltd.), a 130 ⁇ m thick adhesive tape (ASF-110, manufactured by Chuko Flow) was attached so that a space of 24 mm wide ⁇ 300 mm long was formed. In this space, the active energy ray-curable composition is applied, and another release PET film (K1504, manufactured by Toyobo Co., Ltd.) is placed thereon. Then, the active energy ray-curable composition is applied using a laminating roller. Stretched.
- the active energy ray-curable composition was cured by irradiating 3000 mJ / cm 2 of ultraviolet rays onto the release PET film using an ultraviolet irradiation device HTE-3000B INTEGRATOR 814M (manufactured by HI-TECH), and then released.
- the mold PET film was peeled off to obtain a coating film. It was 132 micrometers when the thickness of the coating film was measured using the thickness gauge.
- the mass (M1) of the obtained coating film was weighed and then immersed in toluene. After 24 hours, the membrane was taken out, further washed with toluene, and then the toluene was removed with a vacuum dryer.
- the mass (M2) of the coating film after removing toluene was weighed, and the value of (M2 / M1) ⁇ 100 was taken as the gel fraction (%).
- Adhesion test A 130 ⁇ m thick adhesive tape (ASF-110, manufactured by Chuko Flow) was attached on a stainless steel plate so that a space of width 24 mm ⁇ length 300 mm was formed. An active energy ray-curable liquid composition is applied to this space, and a PET film (E5000, manufactured by Toyobo Co., Ltd.) having a thickness of 50 ⁇ m is further placed thereon. Then, the active energy ray-curable composition is applied using a laminating roller. Stretched.
- the active energy ray-curable composition was cured by irradiating the PET film with ultraviolet rays of 3000 mJ / cm 2 using an ultraviolet irradiation device HTE-3000B INTEGRATOR 814M (manufactured by HI-TECH) to obtain a coating film.
- the coating film and the PET film were cut out along the adhesive tape with a cutter knife to prepare a test piece having a width of 24 mm and a length of 300 mm.
- test piece was at an ambient temperature of 23 ° C., a relative humidity of 30%, a peeling angle of 180 °, and a tensile speed of 300 mm.
- Tensile under the condition of / min, and the force required to peel from the stainless steel plate was measured and defined as the adhesive strength (adhesive strength before wet heat treatment).
- the test piece prepared in the same manner was held for 30 minutes under the conditions of an atmospheric temperature of 160 ° C. and a relative humidity of 90%, and then the adhesive strength was measured in the same manner (adhesive strength after wet heat treatment).
- the active energy ray-curable composition was cured by irradiating the PET film with ultraviolet rays at 3000 mJ / cm 2 using an ultraviolet irradiation device HTE-3000B INTEGRATOR 814M (manufactured by HI-TECH). After the ultraviolet irradiation, the coating film and the PET film were cut along the adhesive tape with a cutter knife, and the release PET film was peeled off to prepare a test piece having a width of 12 mm and a length of 150 mm.
- step (1) 2.61 ml (10.4 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as dimethacrylate (2) and 14.4 ml (135.2 mmol) of methyl methacrylate as monomethacrylate
- step (3) 2.61 ml (10.4 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as dimethacrylate (2) and methacrylic acid as monomethacrylate were added in step (3).
- Polymerization was carried out in the same manner as in Example 5, except that 17.0 ml of a mixture with 14.4 ml (135.2 mmol) of methyl acid was added.
- the consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step (1) was 100%.
- Mn of the polymer obtained at the process (1) was 6,480, and Mw / Mn was 1.12.
- the initiator efficiency (F1) in the step (1) was 95%.
- the consumption rate of methyl methacrylate and n-butyl acrylate in step (2) was 100%.
- Mn of the block copolymer obtained at the process (2) was 26,900, and Mw / Mn was 1.19.
- the block efficiency (F2) from step (1) to step (2) was 70%.
- the consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step (3) was 100%.
- Mn of the obtained block copolymer (X) was 36,200, and Mw / Mn was 1.24.
- an active energy ray-curable composition was prepared in the same manner as in Example 5, and a UV curable test, an adhesive strength test, and a holding power test were performed. The test results are shown in Table 2.
- n-butyl acrylate When the consumption rate of n-butyl acrylate was 95%, 57.0 g of toluene, 0.466 g of copper chloride, 19.7 g of methyl methacrylate, and 1.35 g of 2-hydroxyethyl methacrylate were added. Triamine was added as appropriate to adjust the reaction rate. When the consumption rate of methyl methacrylate was 82% and the consumption rate of 2-hydroxyethyl methacrylate was 100%, 71.4 g of toluene was added and the reaction was stopped by cooling. To the polymerization reaction liquid, 1.07 g of p-toluenesulfonic acid monohydrate was added and stirred at room temperature for 3 hours.
- the obtained (meth) acrylic block copolymer had Mn of 111,000 and Mw / Mn of 1.37.
- an active energy ray curable composition was prepared in the same manner as in Example 5, and a UV curable test, an adhesive strength test, and a holding power test were performed. .
- the test results are shown in Table 2.
- Example 5 and Example 6 are placed under wet heat conditions, it can be seen that their adhesive strength and holding power are greatly reduced and are excellent in wet heat decomposability.
- the adhesive strength and holding strength of the test piece of Comparative Example 1 hardly change even under wet heat conditions, indicating that the wet heat decomposability is extremely low.
- block copolymer (X) of the present invention is excellent in wet heat decomposability.
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Abstract
Description
[1]下記一般式(1)
(式中、R1はメチル基を表し、R2及びR3はそれぞれ独立して炭素数1~6の炭化水素基を表し、nは1~5の整数を表す)で示される活性エネルギー線硬化性基を少なくとも1つ以上有するメタクリル系重合体ブロック(A)と、活性エネルギー硬化性基を有さない(メタ)アクリル系重合体ブロック(B)からなる、(メタ)アクリル系ブロック共重合体(以下、「ブロック共重合体(X)」と称する);
Al-O-Ar (3)
(式中、Arは芳香族環を表す)
で示される化学構造を分子中に含む第3級有機アルミニウム化合物並びにエーテルおよび第3級ポリアミンからなる群から選ばれる少なくとも1種のルイス塩基の存在下でアニオン重合する工程(1);と、
前記第一工程の後に、モノ(メタ)アクリレートを添加し、アニオン重合する工程(2);
とを含む、前記ブロック共重合体(X)の製造方法;
前記工程(1)の後に、モノメタクリレートを添加し、アニオン重合する工程(2-1);と、
前記工程(2-1)の後に、モノアクリレートを添加し、アニオン重合する工程(2-2);
とを含む、上記[2]のブロック共重合体(X)の製造方法;
をさらに含む、上記[2]または[3]のブロック共重合体(X)の製造方法;並びに
ブロック共重合体(X)は、下記一般式(1)
該置換基としては、該活性エネルギー線硬化性基の活性エネルギー線硬化性および湿熱分解性を阻害しないものであればよく、例えば、メトキシ基、エトキシ基、イソプロポキシ基、t-ブトキシ基等のアルコキシ基;塩素原子、臭素原子等のハロゲン原子等が挙げられる。
Al-O-Ar (3)
(式中、Arは芳香族環を表す)
で示される化学構造を分子中に含む第3級有機アルミニウム化合物並びにエーテルおよび第3級ポリアミンからなる群から選ばれる少なくとも1種のルイス塩基の存在下でアニオン重合する工程(1)を含む。
AlR4(R5) (R6) (3-1)
(式中、R4は一価の飽和炭化水素基、一価の芳香族炭化水素基、アルコキシ基、アリールオキシ基またはN,N-二置換アミノ基を表し、R5およびR6はそれぞれ独立してアリールオキシ基又は互いに結合してアリーレンジオキシ基を表す)で示される第3級有機アルミニウム化合物(以下、アルミニウム化合物(3-1)と称する)または下記一般式(3-2)
AlR7(R8) (R9) (3-2)
(式中、R7はアリールオキシ基を表し、R8およびR9はそれぞれ独立して一価の飽和炭化水素基、一価の芳香族炭化水素基、アルコキシ基またはN,N-二置換アミノ基を表す)で示される第3級有機アルミニウム化合物(以下、アルミニウム化合物(3-2)と称する)を使用することが好ましく、アルミニウム化合物(3-1) を使用することがより好ましい。
前記工程(2-1)の後に、モノアクリレートを添加し、アニオン重合する工程(2-2);
とを含むことが好ましい。
不活性重合体の分子量が400以上であることで、活性エネルギー線硬化性組成物の硬化物から該不活性重合体が経時的に流出せず、初期の物性を長期にわたり維持できる。また、不活性重合体の分子量が15,000以下であることで、活性エネルギー線硬化性組成物の取り扱い性がよくなる傾向がある。
不活性重合体の分子量分布は特に限定されないが、通常1.8未満であり、1.7以下が好ましく、1.6以下がより好ましく、1.5以下がさらに好ましく、1.4以下が特に好ましく、1.3以下が最も好ましい。
紫外線照射には、150~450nm波長域の光を発する高圧水銀ランプ、超高圧水銀灯、カーボンアーク灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、LED等を用いることができる。活性エネルギー線の積算光量は、通常10~20000mJ/cm2の範囲であり、30~5000mJ/cm2の範囲が好ましい。10mJ/cm2より少ないと活性エネルギー線硬化性組成物の硬化性が不十分となり、20000mJ/cm2より多いと活性エネルギー線硬化性組成物が劣化するおそれがある。
上記湿熱分解法を行う相対湿度(湿熱分解相対湿度)は10~100%が好ましく、30~100%がより好ましい。
上記湿熱分解法に要する時間(湿熱分解時間)は、1分間~24時間が好ましく、1分間~5時間がより好ましく、1分間~2時間がさらに好ましい。
具体的には、
ポリプロピレン用、金属用、木材用等の粘接着剤(ホットメルト接着剤、光硬化性接着剤);
ハードディスクドライブ(HDD)用、建築用、自動車用、フレキシブルプリンテッドエレクトロニクス用電気・電子部品(太陽電池裏面等)用等のシーリング材;
HDD用、建築用、自動車用、フレキシブルプリンテッドエレクトロニクス用、電気・電子部品(太陽電池裏面等)用などの防錆・防湿・防水用等の封止材;
電線・ケーブル用絶縁被覆材等の電気絶縁材料;
金属蒸着膜アンダーコート、ハードコート、光ファイバコート等のコーティング材;
LED硬化性インク、UV硬化性インク、電子線硬化性インク、インクジェット機器用等のインク;
自動車用、鉄道車両、航空機、工業用のガスケット、パッキン類、防振ゴム、防舷材、ガラスの振動防止材、網入りガラスや合わせガラス端面(切断部)の封止材、ウインドシールガスケット、ドアガラス用ガスケットなどの気密保持用シール材;
エンジンルーム、計測ルーム用制振材等の船舶用途;
エンジン(オイルパン、フロントカバー、ロッカーカバー)、車体(ダッシュ、フロア、ドア、ルーフ、パネル、ホイルハウス)、タランスミッション、パーキングブレーキカバー、シートバック用制振材等の自動車用途;
防振、防音用のエンジン及びサスペンジョンゴム(特にエンジンマウントラバー)等のシャーシ部品;
冷却用、燃料供給用、排気制御用等のホース類、エンジンオイル用シール材等のエンジン部品;
排ガス清浄装置部品;
ブレーキ部品;
家電用のパッキン、Oリング、ベルト等(照明器具用の飾り類、防水パッキン類、防振ゴム類、防虫パッキン類、クリーナ用の防振・吸音と空気シール材、電気温水器用の防滴カバー、防水パッキン、ヒータ部パッキン、電極部パッキン、安全弁ダイアフラム、酒かん器用のホース類、防水パッキン、電磁弁、スチームオーブンレンジ及びジャー炊飯器用の防水パッキン、給水タンクパッキン、吸水バルブ、水受けパッキン、接続ホース、ベルト、保温ヒータ部パッキン、蒸気吹き出し口シール等、燃焼機器用のオイルパッキン、Oリング、ドレインパッキン、加圧チューブ、送風チューブ、送・吸気パッキン、防振ゴム、給油口パッキン、油量計パッキン、送油管、ダイアフラム弁、送気管等、音響機器用のスピーカーガスケット、スピーカーエッジ、ターンテーブルシート、ベルト、プーリー等);
建築分野用の、構造用ガスケット(ジッパーガスケット)、空気膜構造屋根材、防水材、定形シーリング材、防振材、防音材、セッティングブロック、摺動材等;
スポ―ツ用の、スポーツ床(全天候型舗装材、体育館床等)、スポーツシューズ部材(靴底材、中底材等)、球技用ボール(ゴルフボール等);
ルーフ、フロア、シャッタ、カーテンレール、床、配管ダクト、デッキプレート、カーテンウォール、階段、ドア、免振アイソレーター、構造材用制振材等の建築用途;
土木分野用の、構造用材料(ゴム伸縮継手、支承、止水板、防水シート、ラバーダム、弾性舗装、防振パット、防護体等)、工事副材料(ゴム型枠、ゴムパッカー、ゴムスカート、スポンジマット、モルタルホース、モルタルストレーナ等)、工事補助材料(ゴムシート類、エアホース等)、安全対策商品(ゴムブイ、消波材等)、環境保全商品(オイルフェンス、シルトフェンス、防汚材、マリンホース、ドレッジングホース、オイルスキマー等)等;
液晶ディスプレイ、カラーPDP(プラズマディスプレイ)、プラズマアドレス液晶(PALC)ディスプレイ、有機EL(エレクトロルミネッセンス)ディスプレイ、有機TFT(有機薄膜トランジスタ)ディスプレイ、フィールドエミッションディスプレイ(FED)、電子ペーパー、タッチパネル、携帯電話のディスプレイ、カーナビのディスプレイなどのディスプレイ用の封止材、光学弾性樹脂(OCR)、充填材;
ビデオディスク(VD)、CD、CD-ROM、CD-R、CD-RW、DVD、DVD-ROM、DVD-R、DVD-RW、BD、BD-ROM、BD-R、BD-RE、MO、MD、相変化ディスク(PD)、ホログラム、光カード用のディスク基板材料、ピックアップレンズ、保護フィルム、封止材、接着剤;
光学機器(スチルカメラ、ビデオカメラ、プロジェクター、光センサ)のレンズ、ファインダプリズム、光ファイバ、ターゲットプリズム、ファインダーカバー、受光センサー部、保護フィルム、フェルール、封止材、接着剤;
素子の封止材、前面ガラスの保護フィルム、接着剤などの太陽電池部材;
ステッピングモーター、磁気ディスク、ハードディスク、食器洗浄機、乾燥機、洗濯機、ファンヒーター、ミシン、自動販売機、スピーカフレーム、BSアンテナ、VTRカバー用制振材等の電気・電子機器用途;
テレビカメラ、複写機、電算機、プリンタ、レジスタ、キャビネット用制振材等のカメラ・事務機器用途;
光電子集積回路(OEIC)周辺の基板材料;
ヒートスプレッダー;
発熱材料とヒートスプレッダー、ヒートスプレッダーと冷却部材、との間にある熱を伝えるサーマルインターフェイス;
ヒーター、温度センサ、CPU、トランジスタなどの電子部品等の高温部品;
放熱フィン等のヒートシンク等、グラファイトシート(グラファイトフィルム)、液体セラミックスやペルチェ素子等の冷却部材;
熱伝導性材料;
家電、自動車周辺のエレクトロニクス分野(回路のパターン形成、プリント基板上の半田付け時の耐熱被覆等用等)等で用いる半導体回路用の半導体レジスト(UVレジスト、DeepUVレジスト、EBレジスト、電着レジスト、ドライフィルムレジスト);
プリント配線基板用の液状ソルダーレジスト;
プリント基板、ビルドアップ基板、立体回路基板用の電着レジスト;
片面・両面・多層基板の回路形成用のドライフィルムレジスト;
TFT配線用、カラーフィルター用等の液晶用フォトレジスト等;
絶縁コーティングの様な永久レジスト用途;等のレジスト用途;
半導体向けダイシングテープ用、ダイボンディングテープ用の粘接着剤;
LSI、超LSI材料用のマイクロリソグラフィー用のレジスト材料;
LEDの封止材、ダイボンド材、リフレクターや放熱性能を備えた基板上にLEDを配置した基板の封止材;
装飾ディスプレイ用照明;
標識類;
シュータ、エレベータ、エスカレータ、コンベア、トラクタ、ブルドーザ、発電機、コンプレッサ、コンテナ、ホッパ、防音ボックス、草刈り機のモータカバー用制振材等の産業機械関係用途;鉄道車両ルーフ、側板、ドア、アンダーフロア、各種補機カバー、橋梁用制振材等の鉄道用途;半導体用途の精密除振装置用制振材等の防振・制振・防音・免震材料;
断熱材、クッション材、吸音材、防振材、人工皮革、注型材料、成形材料、ポッティング材等の発泡剤;
ゴルフシャフト釣り竿およびボート等のレジャー用途、繊維強化プラスチック(FRP)用途、自動車、航空機、宇宙用途等、回転機・変圧器・制御器の層間材絶縁用途、工業製品及び電子部品接着用等に用いるプリプレグ;
等が挙げられる。
重合後の各モノマーの消費率は、重合反応液0.5mlを採取してメタノール0.5ml中に入れて混合後、該混合液からから0.1mlを採取して、重クロロホルム0.5mlに溶解させて1H-NMR(JEOL製ECX400、測定温度=25℃)を測定した結果から算出した。
得られた重合体のGPC(ゲルパーミュエーションクロマトグラフィー、HLC-8220GPC(東ソー製)、カラム:TSK-gel SuperMultiporeHZ-M(東ソー製)(カラム径=4.6mm、カラム長=15cm)、測定条件:流速=0.35ml/分、温度=40℃、溶離液=テトラヒドロフラン)を測定し、標準ポリスチレン換算の数平均分子量(Mn)および分子量分布(Mw/Mn)を求めた。
実際に工程(1)で得られた重合体の数平均分子量をMn(R1)とし、理論的に工程(1)で得られる重合体の数平均分子量をMn(I1)とすると、工程(1)における開始剤効率(F1)は以下の式から算出される。
F1(%)=100×Mn(R1)/Mn(I1)
実際に工程(2)で得られたブロック共重合体(X)の数平均分子量をMn(R2)とし、理論的に工程(2)で得られるブロック共重合体(X)の数平均分子量をMn(I2)とすると、工程(1)から工程(2)にかけてのブロック効率(F2)は以下の式から算出される。
F2(%)=10000・{Mn(R2)-Mn(R1)}/[F1・{Mn(I2)-Mn(I1)}]
内部を乾燥し、窒素置換した300mlのフラスコに、トルエン100mlを添加したのち、フラスコ内の溶液を攪拌しながら、ルイス塩基として1,1,4,7,10,10-ヘキサメチルトリエチレンテトラミン0.78ml(2.86mmol)、第3級有機アルミニウム化合物としてイソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウムの0.450mol/Lトルエン溶液を12.7ml順次添加したのち、-20℃に冷却した。これに有機リチウム化合物としてsec-ブチルリチウムの1.30mol/Lシクロヘキサン溶液2.00mlを加え、ジメタクリレート(2)として1,1-ジメチルプロパン-1,3-ジオールジメタクリレート2.47ml(10.4mmol)と、モノメタクリレートとしてメタクリル酸メチル1.11ml(10.4mmol)との混合物3.58mlを一括で添加し、アニオン重合を開始した。混合物の添加終了後、10分後に、重合反応液は当初の黄色から無色に変わった。さらに10分撹拌後に、得られた工程(1)の反応液をサンプリングした。
引き続き、得られた前記工程(1)の反応液を-20℃で撹拌しつつ、工程(1)の重合開始から20分後に、モノメタクリレートとしてメタクリル酸メチル2.22ml(20.8mmol)を一括で添加し、100分後にモノアクリレートとしてアクリル酸n-ブチル37.4ml(260mmol)を1ml/分の速度で添加した。アクリル酸n-ブチルを添加終了直後に、工程(2)の反応液をサンプリングした。
引き続き、得られた工程(2)の反応液を撹拌しつつ、-20℃でメタノールを10.0ml添加することにより、アニオン重合を停止させた。得られた溶液を1リットルのメタノール中に注ぎ、生成したブロック共重合体(X)を沈殿させ、回収した。
工程(1)における1,1-ジメチルプロパン-1,3-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。また、工程(1)で得られた重合体のMnは1,500、Mw/Mnは1.13であった。さらに、工程(1)における開始剤効率(F1)は91%であった。
工程(2)におけるメタクリル酸メチルおよびアクリル酸n-ブチルの消費率は100%であった。また、得られたブロック共重合体(X)のMnは24,700、Mw/Mnは1.21であった。さらに、工程(1)から工程(2)にかけてのブロック効率(F2)は65%であった。結果を表1に示す。
実施例1と同様にして工程(1)の反応液を得た後、引き続き、工程(1)の重合開始から120分後に、モノアクリレートとしてアクリル酸n-ブチル37.4ml(260mmol)を-20℃で1ml/分の速度で反応液中に添加した。アクリル酸n-ブチルの添加終了直後に、工程(2)の反応液をサンプリングした。
引き続き、得られた工程(2)の反応液を撹拌しつつ、-20℃でメタノールを10.0ml添加することにより、アニオン重合を停止させた。得られた溶液を1リットルのメタノール中に注ぎ、生成したブロック共重合体(X)を沈殿させ、回収した。
工程(1)における1,1-ジメチルプロパン-1,3-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。また、工程(1)で得られた重合体のMnは1,520、Mw/Mnは1.15であった。さらに、工程(1)における開始剤効率(F1)は90%であった。
工程(2)におけるアクリル酸n-ブチルの消費率は100%であった。また、得られたブロック共重合体(X)のMnは41,700、Mw/Mnは1.20であった。さらに、工程(1)から工程(2)にかけてのブロック効率(F2)は34%であった。結果を表1に示す。
工程(1)において、ジメタクリレート(2)として1,1-ジメチルブタン-1,4-ジオールジメタクリレート2.61ml(10.4mmol)と、モノメタクリレートとしてメタクリル酸メチル1.11ml(10.4mmol)との混合物3.72mlを添加する以外は、実施例1と同様の操作で重合を行った。
工程(1)における1,1-ジメチルブタン-1,4-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。また、工程(1)で得られた重合体のMnは1,420、Mw/Mnは1.14であった。さらに、工程(1)における開始剤効率(F1)は99%であった。
工程(2)におけるメタクリル酸メチルおよびアクリル酸n-ブチルの消費率は100%であった。また、得られたブロック共重合体(X)のMnは16,900、Mw/Mnは1.15であった。さらに、工程(1)から工程(2)にかけてのブロック効率(F2)は85%であった。結果を表1に示す。
工程(1)において、ジメタクリレート(2)として1,1-ジメチルブタン-1,4-ジオールジメタクリレート2.61ml(10.4mmol)と、モノメタクリレートとしてメタクリル酸メチル1.11ml(10.4mmol)との混合物3.72mlを添加する以外は、実施例2と同様の操作で重合を行った。
工程(1)における1,1-ジメチルブタン-1,4-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。また、工程(1)で得られた重合体のMnは1,580、Mw/Mnは1.16であった。さらに、工程(1)における開始剤効率(F1)は90%であった。
工程(2)におけるn-ブチルアクリレートの消費率は100%であった。また、得られたブロック共重合体(X)のMnは29,200、Mw/Mnは1.27であった。さらに、工程(1)から工程(2)にかけてのブロック効率(F2)は50%であった。結果を表1に示す。
DMA-G1:1,1-ジメチルプロパン-1,3-ジオールジメタクリレート
DMA-G2:1,1-ジメチルブタン-1,4-ジオールジメタクリレート
MMA:メタクリル酸メチル
nBA:アクリル酸n-ブチル
実施例1と同様にして工程(2)の反応液を得た後、引き続き、工程(2)の反応液を撹拌しつつ、n-ブチルアクリレート添加直後に、-20℃でジメタクリレート(2)として1,1-ジメチルプロパン-1,3-ジオールジメタクリレート2.47ml(10.4mmol)と、モノメタクリレートとしてメタクリル酸メチル1.11ml(10.4mmol)との混合物3.58mlを一括で添加したのち、5℃/分の速度で0℃に昇温した。混合物の添加から120分後に工程(3)の反応液をサンプリングした。
引き続き、得られた工程(3)の反応液を撹拌しつつ、メタノールを10.0ml添加することにより、アニオン重合を停止させた。得られた溶液を1リットルのメタノール中に注ぎ、生成したブロック共重合体(X)を沈殿させ、回収した。
工程(3)における1,1-ジメチルプロパン-1,3-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。また、得られたブロック共重合体(X)のMnは26,300、Mw/Mnは1.22であった。
得られたブロック共重合体(X)を反応性希釈剤(光重合性単量体)としてメタクリル酸ジシクロペンテニルオキシエチル(FA-512M、日立化成製)に溶解し、70質量%溶液とした。得られた溶液に光重合開始剤である1-ヒドロキシシクロヘキシルフェニルケトンを溶液状態で5質量部配合し、活性エネルギー線硬化性組成物を得た。
(UV硬化性試験)
離型PETフィルム(K1504、東洋紡製)の離型面上に厚さ130μmの粘着テープ(ASF-110、チューコーフロー製)を、幅24mm×長さ300mmのスペースができるように貼り付けた。このスペースに、活性エネルギー線硬化性組成物を塗布し、さらにその上に別の離型PETフィルム(K1504、東洋紡製)を置いたのち、ラミネートローラーを用いて該活性エネルギー線硬化性組成物を延伸した。次いで、紫外線照射装置HTE-3000B INTEGRATOR814M(HI-TECH社製)を用いて、離型PETフィルム上に紫外線を3000mJ/cm2照射することで活性エネルギー線硬化性組成物を硬化させたのち、離型PETフィルムを剥がして、塗膜を得た。塗膜の厚みを厚みゲージを用いて測定したところ132μmであった。得られた塗膜の質量(M1)を秤量した後、トルエンに浸漬し、24時間経過後、膜を取り出し、さらにトルエンで洗浄後、真空乾燥機にてトルエンを除去した。トルエンを除去した後の塗膜の質量(M2)を秤量し、(M2/M1)×100の値をゲル分率(%)とした。
ステンレス板上に厚さ130μmの粘着テープ(ASF-110、チューコーフロー製)を、幅24mm×長さ300mmのスペースができるように貼り付けた。このスペースに活性エネルギー線硬化性液状組成物を塗布し、さらにその上に厚さ50μmのPETフィルム(E5000、東洋紡製)を置いたのち、ラミネートローラーを用いて該活性エネルギー線硬化性組成物を延伸した。次いで、紫外線照射装置HTE-3000B INTEGRATOR814M(HI-TECH社製)を用いて、PETフィルム上に紫外線を3000mJ/cm2照射することで活性エネルギー線硬化性組成物を硬化させて塗膜を得た。カッターナイフで粘着テープに沿って塗膜およびPETフィルムを切り取り、幅24mm×長さ300mmの試験片を作成した。
JISZ-0237に準じて、卓上形精密万能試験機AGS-X(島津製作所製)を用いて、得られた試験片を雰囲気温度23℃、相対湿度30%で、剥離角度180°、引張速度300mm/分の条件で引張り、ステンレス板から剥離するのに要する力を測定し、粘着力とした(湿熱処理前の粘着力)。
同様に作成した試験片を、雰囲気温度160℃、相対湿度90%の条件で30分間保持したのち、同様に粘着力を測定した(湿熱処理後の粘着力)。
離型PETフィルム(K1504、東洋紡製)の離型面上に厚さ130μmの粘着テープ(ASF-110、チューコーフロー製)を、幅12mm×長さ150mmのスペースができるように貼り付けた。このスペースに、活性エネルギー線硬化性組成物を塗布し、さらにその上に厚さ50μmのPETフィルム(E5000、東洋紡製)を置いたのち、ラミネートローラーを用いて該活性エネルギー線硬化性組成物を延伸した。次いで、紫外線照射装置HTE-3000B INTEGRATOR814M(HI-TECH社製)を用いて、PETフィルム上に紫外線を3000mJ/cm2照射することで活性エネルギー線硬化性組成物を硬化させた。紫外線照射後に、カッターナイフで粘着テープに沿って塗膜およびPETフィルムを切り取り、離型PETフィルムを剥がすことで、幅12mm×長さ150mmの試験片を作成した。
JISZ-0237に準じて、保持力試験機145-D(安田精機製作所製)を用いて、雰囲気温度60℃、相対湿度30%で、1kgf(9.8N)荷重で引張り、試験片がステンレス板から剥離するまでの時間を測定した(湿熱処理前の保持力)。
同様に作成した試験片を、雰囲気温度160℃、相対湿度90%の条件で30分間保持したのち、同様に保持力を測定した(湿熱処理後の保持力)。
工程(1)において、ジメタクリレート(2)として1,1-ジメチルプロパン-1,3-ジオールジメタクリレート2.61ml(10.4mmol)と、モノメタクリレートとしてメタクリル酸メチル14.4ml(135.2mmol)との混合物17.0mlを添加し、工程(3)において、ジメタクリレート(2)として1,1-ジメチルプロパン-1,3-ジオールジメタクリレート2.61ml(10.4mmol)と、モノメタクリレートとしてメタクリル酸メチル14.4ml(135.2mmol)との混合物17.0mlを添加する以外は、実施例5と同様の操作で重合を行った。
工程(1)における1,1-ジメチルプロパン-1,3-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。また、工程(1)で得られた重合体のMnは6,480、Mw/Mnは1.12であった。さらに、工程(1)における開始剤効率(F1)は95%であった。
工程(2)におけるメタクリル酸メチルおよびアクリル酸n-ブチルの消費率は100%であった。また、工程(2)で得られたブロック共重合体のMnは26,900、Mw/Mnは1.19であった。さらに、工程(1)から工程(2)にかけてのブロック効率(F2)は70%であった。
工程(3)における1,1-ジメチルプロパン-1,3-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。また、得られたブロック共重合体(X)のMnは36,200、Mw/Mnは1.24であった。
得られたブロック共重合体(X)を用いて、実施例5と同様に、活性エネルギー線硬化性組成物を調製し、UV硬化性試験、粘着力試験、保持力試験をそれぞれ実施した。試験結果を表2に示す。
内部を乾燥し、窒素置換した300ml耐圧反応器に、臭化銅0.676g、アクリル酸n-ブチル48.3g、アセトニトリル8.47g、2,5-ジブロモアジピン酸ジエチル0.339gを加えて攪拌し、75℃に昇温させた。その後、ペンタメチルジエチレントリアミン( 以下トリアミンと称する) 0.0816gを添加して重合を開始させた。アクリル酸n-ブチルの消費率が95%の時点で、トルエン57.0g、塩化銅0.466g、メタクリル酸メチル19.7g、メタクリル酸2-ヒドロキシエチル1.35gを追加した。トリアミンを適宜追加し、反応速度を調整した。メタクリル酸メチルの消費率が82% 、メタクリル酸2-ヒドロキシエチルの消費率が100%の時点で、トルエン71.4gを追加するとともに冷却して反応を停止させた。
重合反応液に、p-トルエンスルホン酸一水和物1.07gを加えて室温で3時間撹拌した。析出した不溶部を濾過により除いた後、吸着剤キョーワード500SH(協和化学製)2.76gを加えて室温で更に3時間撹拌した。吸着剤を濾過により除き、無色透明の溶液を得た。この溶液を乾燥させて溶剤および残存モノマーを除き、目的のブロック共重合体を得た。得られたブロック共重合体のMnは109,000、Mw/Mnは1.37であった。
ブロック共重合体をトルエンに溶解させ30%溶液とした。300mlセパラブルフラスコに、ブロック共重合体溶液100g、トリエチルアミン1.41gを加え、氷水バスで冷却した。ここに塩化アクリロイル1.25gを滴下し、2時間攪拌した。サンプリングし、1H-NMR測定を行うと、反応率は70%であった。
反応後の溶液から析出したアミン塩を除去するため、吸引ろ過を2回行った。次に、ろ液からトルエンを除去するため、室温で脱揮した。残存するアミン塩を除去するため、クロロホルムと炭酸水素ナトリウム水溶液で分液を行い、水層は廃棄、クロロホルム層は吸引ろ過といった精製を2回繰り返した。次いで、クロロホルムと食塩水で分液を3回行い、精製した。分液による精製後、有機層に硫酸マグネシウムを加え、水分を除去した。最後に、クロロホルムと残存するトリエチルアミン、アクリル酸を除去するために、70℃に加熱を行いながら脱揮を行ってアクリロイル基を有する目的の(メタ)アクリル系ブロック共重合体を得た。得られた(メタ)アクリル系ブロック共重合体のMnは111,000、Mw/Mnは1.37であった。
得られた(メタ)アクリル系ブロック共重合体を用いて、実施例5と同様に、活性エネルギー線硬化性組成物を調製し、UV硬化性試験、粘着力試験、保持力試験をそれぞれ実施した。試験結果を表2に示す。
Claims (5)
- 下記一般式(2)
(式中、R1はメチル基を表し、R2及びR3はそれぞれ独立して炭素数1~6の炭化水素基を表し、nは1~5の整数を表す)で示されるジメタクリレート(2)を5~100モル%を含有するメタクリル酸エステルを、有機リチウム化合物、下記一般式(3)
Al-O-Ar (3)
(式中、Arは芳香族環を表す)
で示される化学構造を分子中に含む第3級有機アルミニウム化合物並びにエーテルおよび第3級ポリアミンからなる群から選ばれる少なくとも1種のルイス塩基の存在下でアニオン重合する工程(1);と、
前記工程(1)の後に、モノ(メタ)アクリレートを添加し、アニオン重合する工程(2);
とを含む、請求項1に記載の(メタ)アクリル系ブロック共重合体の製造方法。 - 前記工程(2)が、
前記工程(1)の後に、モノメタクリレートを添加し、アニオン重合する工程(2-1);と、
前記工程(2-1)の後に、モノアクリレートを添加し、アニオン重合する工程(2-2);
とを含む、請求項2に記載の(メタ)アクリル系ブロック共重合体の製造方法。 - 前記工程(2)の後に、前記一般式(2)で示されるジメタクリレート(2)を5~100モル%含有するメタクリル酸エステルを添加し、アニオン重合する工程(3);
をさらに含む、請求項2または3に記載の(メタ)アクリル系ブロック共重合体の製造方法。 - 請求項1に記載の(メタ)アクリル系ブロック共重合体を含有してなる活性エネルギー線硬化性組成物。
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JP2016037574A (ja) * | 2014-08-08 | 2016-03-22 | 株式会社クラレ | 硬化型接着剤 |
JP2016050270A (ja) * | 2014-09-01 | 2016-04-11 | 株式会社クラレ | (メタ)アクリル系ブロック共重合体および活性エネルギー線硬化性組成物 |
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JP2016056251A (ja) * | 2014-09-08 | 2016-04-21 | 株式会社クラレ | メタクリル樹脂成形体およびその製造方法 |
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JP2017193644A (ja) * | 2016-04-21 | 2017-10-26 | 株式会社クラレ | 活性エネルギー線硬化性組成物とそれを含む積層体および成形体 |
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Cited By (13)
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JP2016037574A (ja) * | 2014-08-08 | 2016-03-22 | 株式会社クラレ | 硬化型接着剤 |
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WO2016027602A1 (ja) * | 2014-08-19 | 2016-02-25 | 株式会社クラレ | 活性エネルギー線硬化性組成物 |
JP2016050270A (ja) * | 2014-09-01 | 2016-04-11 | 株式会社クラレ | (メタ)アクリル系ブロック共重合体および活性エネルギー線硬化性組成物 |
JP2016056251A (ja) * | 2014-09-08 | 2016-04-21 | 株式会社クラレ | メタクリル樹脂成形体およびその製造方法 |
JP2016056312A (ja) * | 2014-09-11 | 2016-04-21 | 株式会社クラレ | 硬化型インク用バインダーおよび硬化型インク |
JP2016210926A (ja) * | 2015-05-12 | 2016-12-15 | 株式会社クラレ | ブロック共重合体ならびにその製造方法および用途 |
WO2017014154A1 (ja) * | 2015-07-22 | 2017-01-26 | 株式会社クラレ | (メタ)アクリル系ブロック共重合体 |
KR20180030853A (ko) | 2015-07-22 | 2018-03-26 | 주식회사 쿠라레 | (메타)아크릴계 블록 공중합체 |
JPWO2017014154A1 (ja) * | 2015-07-22 | 2018-05-10 | 株式会社クラレ | (メタ)アクリル系ブロック共重合体 |
US20180208700A1 (en) * | 2015-07-22 | 2018-07-26 | Kuraray Co., Ltd. | (meth)acrylic block copolymer |
JPWO2017110439A1 (ja) * | 2015-12-25 | 2018-10-11 | 株式会社クラレ | (メタ)アクリル系ブロック共重合体および該(メタ)アクリル系ブロック共重合体を含有する活性エネルギー線硬化性組成物 |
JP2017193644A (ja) * | 2016-04-21 | 2017-10-26 | 株式会社クラレ | 活性エネルギー線硬化性組成物とそれを含む積層体および成形体 |
Also Published As
Publication number | Publication date |
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EP2977392A1 (en) | 2016-01-27 |
KR20150132224A (ko) | 2015-11-25 |
EP2977392A4 (en) | 2016-11-02 |
US20160002378A1 (en) | 2016-01-07 |
US9988477B2 (en) | 2018-06-05 |
TW201441295A (zh) | 2014-11-01 |
KR102088387B1 (ko) | 2020-03-12 |
JP6289445B2 (ja) | 2018-03-07 |
JPWO2014148251A1 (ja) | 2017-02-16 |
EP2977392B1 (en) | 2017-08-16 |
CN105051083A (zh) | 2015-11-11 |
CN105051083B (zh) | 2018-05-15 |
TWI602872B (zh) | 2017-10-21 |
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