WO2015098549A1 - Composition de résine durcissable par ultraviolets et stratifié - Google Patents

Composition de résine durcissable par ultraviolets et stratifié Download PDF

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WO2015098549A1
WO2015098549A1 PCT/JP2014/082858 JP2014082858W WO2015098549A1 WO 2015098549 A1 WO2015098549 A1 WO 2015098549A1 JP 2014082858 W JP2014082858 W JP 2014082858W WO 2015098549 A1 WO2015098549 A1 WO 2015098549A1
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meth
resin composition
compound
curable resin
ultraviolet curable
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PCT/JP2014/082858
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English (en)
Japanese (ja)
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依慶 米山
裕一 松木
丈章 齋木
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横浜ゴム株式会社
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Priority to CN201480075434.6A priority Critical patent/CN106029702A/zh
Priority to KR1020167015417A priority patent/KR20160102986A/ko
Priority to JP2015554734A priority patent/JP6597310B2/ja
Publication of WO2015098549A1 publication Critical patent/WO2015098549A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • 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
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • 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
    • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links

Definitions

  • the present invention relates to an ultraviolet curable resin composition and a laminate having a cured film formed using the same.
  • Patent Document 1 discloses that “(a) a polyfunctional (meth) acrylate and (b) a branch having a trunk made of an acrylic resin”.
  • An ultraviolet curable resin composition comprising a polymer and (c) a diluent solvent, wherein the ultraviolet curable resin composition does not contain a leveling agent, and the diluent solvent is a combination of solvents having different boiling points. ([Claim 1]).
  • the inventors of the present invention have studied the ultraviolet curable resin composition described in Patent Document 1. As a result, the hardness of the resulting cured film was good, but the flexibility was inferior, and the handleability when film-forming was performed. It was clarified that it was difficult to achieve both the hardness and the bending resistance.
  • an object of the present invention is to provide an ultraviolet curable resin composition capable of forming a cured film having both excellent hardness and bending resistance.
  • the present inventors have found that an ultraviolet curable type containing a (meth) acrylic block polymer having a specific block chain together with a polyfunctional (meth) acrylate compound and a photopolymerization initiator.
  • the present inventors have found that the cured film formed using the resin composition has good hardness and bending resistance, and completed the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • the polyfunctional (meth) acrylate compound (A) is a urethane (meth) acrylate (A1) having a urethane bond and two or more (meth) acryloyloxy groups in one molecule.
  • the polyfunctional (meth) acrylate compound (A) is at least two nematic liquid crystalline compounds (A2) having two or more (meth) acryloyloxy groups in one molecule, and two in one molecule.
  • the glass transition temperature of the block chain (b1) is ⁇ 40 to ⁇ 50 ° C.
  • the glass transition temperature of the block chain (b2) is 100 to 120 ° C.
  • the (meth) acrylic block polymer (B) has at least the block chain (b2), the block chain (b1), and the block chain (b2) in this order, and the block chain (b2).
  • R 1 represents a hydrocarbon group which may have a hydrogen atom or a hetero atom
  • R 2 represents a hydrocarbon group which may have a hydrogen atom or a hetero atom.
  • the plurality of R 2 may be the same or different.
  • [7] The ultraviolet curable resin composition according to any one of [1] to [6], further comprising a compound (E) having a benzotriazole skeleton.
  • the nematic liquid crystalline compound (A2) is a compound represented by the following formula (2a), and the chiral agent (A3) is a compound represented by the following formula (3a).
  • the ultraviolet curable resin composition according to any one of [7]. (In formula (2a), n represents an integer of 2 to 5, and in formula (3a), m represents an integer of 2 to 5)
  • the content of the (meth) acrylic block polymer (B) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound (A).
  • the content of the chiral agent (A3) is 1.0 to 30.0% by mass based on the total mass of the nematic liquid crystal compound (A2) and the chiral agent (A3).
  • a resin layer is further provided between the substrate and the cured film, The laminate according to [11], wherein the resin layer is an acrylic resin layer having a surface tension of 32 mN / m or more.
  • the laminate according to [11] or [12] which is used for an electronic image display device or a spectacle lens.
  • an ultraviolet curable resin composition capable of forming a cured film having both excellent hardness and flexibility. Moreover, since the laminated body of this invention has the cured film formed using the ultraviolet curable resin composition of this invention, it can make it compatible with the outstanding hardness and bending resistance.
  • FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.
  • the ultraviolet curable resin composition of the present invention (hereinafter also simply referred to as “the composition of the present invention”) is a polyfunctional (meth) acrylate compound having two or more (meth) acryloyloxy groups in one molecule (A ), A (meth) acrylic block polymer (B), and a photopolymerization initiator (C), and the (meth) acrylic block polymer (B) has a glass transition temperature of 0 ° C. or lower.
  • An ultraviolet curable resin composition having a chain (b1) and a block chain (b2) having a glass transition temperature of 60 ° C. or higher.
  • (meth) acryloyloxy group means an acryloyloxy group (CH 2 ⁇ CHCOO—) or a methacryloyloxy group (CH 2 ⁇ C (CH 3 ) COO—).
  • (meth) acrylic means acrylic or methacrylic.
  • the hardness and bending resistance of the cured film formed by using the composition containing the polyfunctional (meth) acrylate compound (A) and the (meth) acrylic block polymer (B). Property is improved.
  • the block chain (b1) in which the glass transition temperature of the (meth) acrylic block polymer (B) is 0 ° C. or lower contributes to the flexibility of the cured film, and the glass transition temperature.
  • the block chain (b2) having a temperature of 60 ° C. or higher contributes to the maintenance of the rigidity of the cured film, it can impart bending resistance without impairing the excellent hardness expressed by the polyfunctional (meth) acrylate compound. It is thought that it was made.
  • the polyfunctional (meth) acrylate compound (A) contained in the composition of the present invention is not particularly limited as long as it is a compound having two or more (meth) acryloyloxy groups in one molecule.
  • the number of (meth) acryloyloxy groups contained in one molecule of the polyfunctional (meth) acrylic compound (A) improves the coating property of the composition of the present invention and further improves the hardness of the cured film. For reasons, 3 or more are preferable, and 4 to 15 are more preferable.
  • polyfunctional (meth) acrylate compound (A) examples include (meth) acrylic acid ester of polyhydric alcohol, urethane (meth) acrylate (A1) having a urethane bond in the molecule, and nematic liquid crystal compound (A2). And chiral agents (A3) and the like, and these may be used alone or in combination of two or more.
  • urethane (meth) acrylate (A1) is preferable because the curability of the composition of the present invention is improved and the optical properties and hardness of the cured film are further improved.
  • the resulting cured film reflects at least part of light in the blue light region (wavelength region of 385 nm to 495 nm) and exhibits a blue light cut function, so that the nematic liquid crystalline compound (A2) and the chiral agent (A3 ) Is preferably used in combination.
  • the reason why the blue light function is exhibited in this way is that a specific uneven pattern is formed on the surface of the cured film depending on a predetermined orientation (twisted) state of the nematic liquid crystalline compound resulting from the addition of the chiral agent. This is probably because at least part of the light in the region (wavelength region of 385 nm to 495 nm) was reflected. In addition, it is considered that such a reflection can reduce the problem that the yellowishness of the cured film becomes strong due to the reflection of blue light in natural light in spite of having a blue light cut function.
  • polyhydric alcohol (meth) acrylic acid esters include trifunctional groups such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol tri (meth) acrylate; pentaerythritol tetra Tetrafunctional system such as (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol Penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (me
  • urethane (meth) acrylate (A1) examples include a reaction product of a polyhydric alcohol (meth) acrylic acid ester and a polyisocyanate compound.
  • the (meth) acrylic acid ester of the polyhydric alcohol used when producing the urethane (meth) acrylate for example, at least one of the (meth) acrylic acid ester of the polyhydric alcohol described above. What has a hydroxy group is mentioned.
  • polyisocyanate compound used when manufacturing urethane (meth) acrylate for example, tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, Aromatic polyisocyanates such as tolidine diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, Bis (isocyanate methyl) ) Cyclohexane, aliphatic polyisocyanates such as dicyclohexylmethane
  • the nematic liquid crystalline compound (A2) is not particularly limited as long as it is a nematic liquid crystalline compound having two or more (meth) acryloyloxy groups in one molecule.
  • a chiral agent (A3) described later blue light A compound that expresses a cutting function is preferred.
  • nematic liquid crystalline compound for example, a rod-like liquid crystalline compound having two or more (meth) acryloyloxy groups in one molecule is preferable.
  • the nematic liquid crystalline compound is represented by the following formula (I). It is preferable that it is a compound. R 3 -C 3 -D 3 -C 5 -MC 6 -D 4 -C 4 -R 4 ...
  • R 3 and R 4 are (meth) acryloyloxy groups, each independently (meth) acryl group, (thio) epoxy group, oxetane group, thietanyl group, aziridinyl group, pyrrole group, vinyl group, allyl group, fumarate group, cinnamoyl group, an oxazoline group, a mercapto group, iso (thio) cyanate group, an amino group, a hydroxyl group, a carboxyl group, and represents a group selected from the group consisting of alkoxysilyl group .
  • D 3 and D 4 is selected from the group consisting of a single bond, a linear or branched alkyl group having 1 to 20 carbon atoms, and a linear or branched alkylene oxide group having 1 to 20 carbon atoms.
  • nematic liquid crystalline compound represented by the above formula (I) the alignment (twisted) state can be easily adjusted by a chiral agent (A3) described later, and polymerization using a photopolymerization initiator (C) described later can be performed.
  • a compound represented by the following formula (2a) is preferable because it easily proceeds.
  • n represents an integer of 2 to 5
  • nematic liquid crystal compound (A2) other than the compound represented by the above formula (2a) include the following compounds.
  • the chiral agent (A3) is not particularly limited as long as it is a chiral agent having two or more (meth) acryloyloxy groups in one molecule.
  • the blue light cut function It is preferable that the compound expresses.
  • a compound having an isosorbide skeleton structure is preferable, and specifically, a compound represented by the following formula (II) is preferable.
  • P 1 and P 2 each independently represents a hydrocarbon group having 10 to 20 carbon atoms including one 1,4-cyclohexylene group, and the group has an etheric oxygen atom or ester. It may have a bond, and a hydrogen atom in the group may be substituted with a fluorine atom, provided that P 1 and P 2 further include a (meth) acryloyloxy group.
  • the blue light cut function of the cured film cured together with the liquid crystalline compound represented by the above formula (2a) becomes better, so that the following formula (3a) It is preferable that it is a compound represented by these.
  • m represents an integer of 2 to 5.
  • chiral agent (A3) other than the compound represented by the above formula (3a) specifically, for example, a compound represented by the following formula (3b) and a compound represented by the following formula (3c) are preferable. It is mentioned in.
  • Examples of the chiral agent (A3) other than the compounds represented by the above formulas (3a) to (3c) include, for example, JP-A-2005-289881, JP-A-2004-115414, JP-A-2003-66214, Published in JP2003-313187, JP2003-342219, JP2000-290315, JP6-072962, U.S. Pat. No. 6,468,444, WO98 / 00428, etc.
  • Commercially available products such as BASF's Palio Color LC756, ADEKA Kiracol's CNL617R, and CNL-686L can also be used as appropriate.
  • the content of the chiral agent (A3) is the total mass of the nematic liquid crystalline compound (A2) and the chiral agent (A3) because the blue light cut function of the cured film becomes better.
  • the content is preferably 1.0 to 30.0% by mass.
  • the chiral agent (A3) is preferably 4.0 to 6.5% by mass with respect to the total mass of the nematic liquid crystal compound (A2) and the chiral agent (A3).
  • the (meth) acrylic block polymer (B) contained in the composition of the present invention has a block chain (b1) having a glass transition temperature of 0 ° C. or lower and a block chain (b2) having a glass transition temperature of 60 ° C. or higher.
  • the polyfunctional (meth) acrylate compound (A) and the (meth) acrylic block polymer (B) are separate compounds, and the (meth) acrylic block polymer is (meth) acryloyl. When it has two or more oxy groups, it corresponds to the (meth) acrylic block polymer (B).
  • the “block chain having a desired glass transition temperature” means a block chain having a homopolymer glass transition temperature obtained by homopolymerizing monomers constituting the repeating unit of the corresponding block chain.
  • the glass transition temperature is a value measured using a differential thermal analyzer (DSC) manufactured by DuPont in accordance with ASTM D3418-82 at a heating rate of 10 ° C./min.
  • DSC differential thermal analyzer
  • the block chain (b1) is a soft segment having a glass transition temperature of ⁇ 40 to ⁇ 50 ° C.
  • the block chain (b2) is preferably a hard segment exhibiting a glass transition temperature of 100 to 120 ° C.
  • the block polymer having each segment has at least the block chain (b2) [hard segment], the block chain (b1) [soft segment] and the block chain (b2) [hard segment] in this order.
  • the block chain (b2) [hard segment] in total is preferably 20% by mass or more.
  • Such (meth) acrylic block polymer (B) is prepared by living radical polymerization using two or more (meth) acrylate monomers and optionally other ethylenically unsaturated copolymerizable monomers. Block polymers to be used.
  • examples of the monomer constituting the repeating unit of the block chain (b1) include butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, and isononyl acrylate. Etc.
  • a monomer which comprises the repeating unit of the said block chain (b2) among the said (meth) acrylate monomers specifically, for example, lauryl (meth) acrylate, mistyryl (meth) acrylate, and isomustryl (meth) Examples include acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, docosanyl (meth) acrylate, tetracosanyl (meth) acrylate, hexacosanyl (meth) acrylate, and octacosanyl (meth) acrylate.
  • ethylenically unsaturated copolymerizable monomer examples include styrene monomers such as ⁇ -methylstyrene, vinyltoluene, styrene and divinylbenzene; and maleimides such as phenylmaleimide and cyclohexylmaleimide.
  • Monomeric monomers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether; fumaric acid, mono- and dialkyl esters of fumaric acid; maleic acid; mono- and dialkyl esters of maleic acid; Itaconic acid; mono and dialkyl esters of itaconic acid; (meth) acrylonitrile, butadiene, isoprene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ketone, vinyl pyridine, vinyl carbazole, etc.
  • the It may be used in the seed alone or in combination of two or more thereof.
  • the polymerization method of living anionic polymerization using such a monomer is not particularly limited, and a transition metal and its ligand are used as an activator, and the polymerization reaction proceeds in the presence of these using a polymerization initiator.
  • a polymerization initiator an ester having bromine or chlorine at the ⁇ -position or a styrene derivative is suitable. Examples thereof include 2-bromo (or chloro) propionic acid derivatives or chloro (or bromide) 1-phenyl derivatives.
  • methyl 2-bromo (or chloro) propionate 2-bromo (or chloro) Selected from ethyl propionate, methyl 2-bromo (or chloro) -2-propionate, ethyl 2-bromo (or chloro) -2-propionate, 1-phenylethyl chloride (or bromide), ethyl 2-bromoisobutyrate Halogen compounds that can be used can be used.
  • the content of the (meth) acrylic block polymer (B) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound (A).
  • the amount is preferably 1 to 5 parts by mass.
  • the weight average molecular weight of the (meth) acrylic block polymer (B) is determined from the viewpoints of coating properties of the composition of the present invention, the appearance and optical properties of the resulting cured film, and the like.
  • the resulting cured film has better bending resistance and further improved hardness, so that it is preferably 20,000 to 200,000, more preferably 50,000 to 100,000.
  • the weight average molecular weight (Mw) of the (meth) acrylic block polymer (B) is measured in terms of standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
  • a commercially available product can be used as such a (meth) acrylic block polymer (B).
  • a commercially available product can be used as such a (meth) acrylic block polymer (B).
  • Specific examples thereof include Clarity LA-2250 (weight average molecular weight: 85000, manufactured by Kuraray Co., Ltd.), Clarity LA-4285 (weight average molecular weight: 85000, manufactured by Kuraray Co., Ltd.), Clarity LA2140e (weight average molecular weight: 80000, manufactured by Kuraray Co., Ltd.), and the like.
  • the photopolymerization initiator (C) contained in the composition of the present invention is not particularly limited as long as it can polymerize the polyfunctional (meth) acrylate compound (A) by light.
  • Examples of the photopolymerization initiator (C) include acetophenone compounds, benzoin ether compounds, benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like.
  • benzoin benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone Methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1, Carbonyl compounds such as 2-diphenylethane-1-one and 1-hydroxycyclohexyl phenyl ketone; Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Azobis Azo compounds such as sobutyronitrile and azobis
  • 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl are preferred from the viewpoints of light stability, high efficiency of photocleavage, surface curability, compatibility, low volatility, low odor and the like.
  • 2-hydroxy-2-methyl-1-phenyl are preferred from the viewpoints of light stability, high efficiency of photocleavage, surface curability, compatibility, low volatility, low odor and the like.
  • -Propan-1-one 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one is preferred.
  • the content of the photopolymerization initiator (C) is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound (A). More preferably, it is ⁇ 10 parts by mass.
  • Compound (D) having naphthalimide skeleton The composition of the present invention can absorb a region on the low wavelength side (385 to 420 nm) in the blue light region, and the blue light cut function as a whole becomes better.
  • the compound (D) having a phthalimide skeleton is preferably contained.
  • R 1 represents a hydrocarbon group which may have a hydrogen atom or a hetero atom
  • R 2 represents a hydrocarbon group which may have a hydrogen atom or a hetero atom.
  • the plurality of R 2 may be the same or different.
  • hydrocarbon group optionally having a hetero atom represented by R 1 and R 2 in the above formula (1) examples include, for example, an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic Group hydrocarbon groups and combinations thereof, which may have an unsaturated bond.
  • the hydrocarbon group represented by R 1 is preferably a linear or branched alkyl group, and preferably has 1 to 12 carbon atoms.
  • the hydrocarbon group represented by R 2 is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group.
  • the content of the compound (D) having a naphthalimide skeleton is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound (A), and 0.5 to 3 More preferably, it is 0.0 parts by mass.
  • composition of the present invention can absorb the low wavelength region (385 to 430 nm) in the blue light region and improve the blue light cut function as a whole. It is preferable to contain.
  • Examples of the compound (E) having a benzotriazole skeleton include a compound represented by the following formula (4).
  • R 3 represents a hydrogen atom or a hydrocarbon group which may have a hetero atom.
  • Examples of the hydrocarbon group optionally having a hetero atom represented by R 3 in the above formula (4) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like. Combinations may be mentioned and may have an unsaturated bond.
  • Examples of commercially available compounds (E) having such a benzotriazole skeleton include Tinuvin Carbo protect (manufactured by BASF) and Tinuvin ⁇ 384-2 (manufactured by BASF).
  • the content of the compound (E) having a benzotriazole skeleton is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound (A), preferably 0.5 to 3 More preferably, it is 0.0 parts by mass.
  • the composition of the present invention preferably further contains a solvent from the viewpoint of good coatability.
  • a solvent will not be specifically limited if it can melt
  • ketones such as methyl ethyl ketone (MEK), methyl isobutyketone (MIBK), cyclohexanone; alcohols such as propylene glycol monomethyl ether (PGME) and isopropyl alcohol (IPA); cycloalkanes such as cyclohexane; toluene, xylene And aromatic hydrocarbon compounds such as benzyl alcohol.
  • PGME propylene glycol monomethyl ether
  • IPA isopropyl alcohol
  • cycloalkanes such as cyclohexane
  • toluene xylene
  • aromatic hydrocarbon compounds such as benzyl alcohol.
  • cyclohexanone and MIBK are preferred from the viewpoint of excellent solubility, drying properties, and paintability.
  • a solvent can be
  • the content of an arbitrary solvent is preferably 85 to 5% by mass in the total amount of the composition from the viewpoint of coating properties.
  • the composition of the present invention preferably further contains a leveling agent because the blue light cut function of the cured film becomes better.
  • a leveling agent examples include silicone leveling agents, acrylic leveling agents, vinyl leveling agents, and fluorine leveling agents. Among these, it is preferable to use an acrylic leveling agent because the uniformity of the cured film is improved and, as a result, the transparency of the cured film is improved.
  • the content of an arbitrary leveling agent is preferably 0.01 to 3% by mass in the total amount of the composition from the viewpoint of coatability.
  • composition of the present invention is, for example, an ultraviolet absorber, a filler, an anti-aging agent, an antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, an antioxidant, Additives such as foaming agents, matting agents, light stabilizers, dyes, pigments can be further contained.
  • the production method of the composition of the present invention is not particularly limited, and the above-described polyfunctional (meth) acrylate compound (A), (meth) acrylic block polymer (B), photopolymerization initiator (C), and any compound ( D), a compound (E), a solvent, a leveling agent, and an additive can be manufactured by mixing uniformly.
  • the laminate of the present invention is a laminate having a substrate and a cured film, and the cured film is formed using the above-described composition of the present invention. Since the laminated body of this invention has a cured film formed using the composition of this invention, it is excellent in a blue light cut function.
  • the laminated body 100 shown in FIG. 1 has the base material 102 and the cured film 104 formed using the composition of this invention.
  • the thickness of the substrate and the cured film is not particularly limited, but the thickness of the substrate is preferably about 50 to 300 ⁇ m, and the thickness of the cured film is preferably about 0.1 to 100 ⁇ m. .
  • the said base material is not specifically limited, As a constituent material, plastics, rubber
  • the plastic may be either a thermosetting resin or a thermoplastic resin. Specific examples thereof include polyethylene terephthalate (PET), cycloolefin polymer (homopolymer, copolymer, hydrogenated). For example, COP and COC), polymethyl methacrylate resin (PMMA resin), polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, polyamide resin, etc. Is mentioned.
  • the base material may be subjected to a surface treatment such as a corona treatment.
  • the form of the substrate is not particularly limited, but is preferably a film.
  • COC is a copolymer (cycloolefin copolymer) of tetracyclododecene and an olefin such as ethylene.
  • COP is a polymer (cycloolefin polymer) obtained by ring-opening polymerization of norbornene and hydrogenation. Examples of COC and COP structures are shown below.
  • the orientation (twist) state of the liquid crystal compound constituting the cured film becomes good, and the adhesiveness with the base material is also good. Further, it is preferable to have a resin layer.
  • the resin layer is preferably an acrylic resin layer having a surface tension of 32 mN / m or more.
  • the surface tension is applied to the cured acrylic resin layer with a wet pen (8 sets of pen numbers 30, 32, 34, 36, 38, 40, 42 and 44 mN / m, manufactured by Alcotest).
  • a wet pen 8 sets of pen numbers 30, 32, 34, 36, 38, 40, 42 and 44 mN / m, manufactured by Alcotest.
  • an acrylic resin layer has a surface tension of 32 mN / m or more, it is abbreviated as, for example, an ultraviolet curable resin composition (hereinafter referred to as “hard coat resin composition”) used in a conventionally known hard coat. ) Is preferably an acrylic resin layer formed using The surface tension can be adjusted by adding a conventionally known leveling agent.
  • the resin composition for hard coat for example, a composition containing a polyfunctional (meth) acrylate (a) and a photopolymerization initiator (b) described later can be used.
  • the said polyfunctional (meth) acrylate (a) can select and use the thing similar to the said polyfunctional (meth) acrylate compound (A) which the composition of this invention contains suitably.
  • the photopolymerization initiator (b) is not particularly limited as long as it can polymerize the polyfunctional (meth) acrylate (a) by light, and the photopolymerization contained in the composition of the present invention.
  • a thing similar to an initiator (C) can be selected suitably, and can be used.
  • the hard coat resin composition is, for example, an ultraviolet absorber, a filler, an anti-aging agent, an antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, and an antioxidant as long as the object of the present invention is not impaired. Further, additives such as an antifoaming agent, a leveling agent, a matting agent, a light stabilizer, a dye and a pigment can be further contained. Examples of the leveling agent include silicone leveling agents, acrylic leveling agents, vinyl leveling agents, and fluorine leveling agents.
  • the thickness of the resin layer is preferably about 0.1 to 100 ⁇ m, more preferably 1 to 5 ⁇ m, because the adhesion between the substrate and the cured film becomes better. .
  • the laminate of the present invention may have a hard coat layer on the surface of the cured film opposite to the substrate.
  • the hard coat layer is preferably an acrylic resin layer formed using the hard coat resin composition described in the resin layer described above, and the formation method thereof is the same as the resin layer formation method described above. A similar method can be mentioned.
  • the thickness of the hard coat layer is not particularly limited, but is preferably about 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m.
  • the method for producing a laminate of the present invention includes, for example, a step of coating the composition of the present invention on a film-like substrate (or the above resin layer if the resin layer is provided), drying, and irradiating ultraviolet rays The method which has this is mentioned.
  • the method of coating the composition of the present invention on the substrate is not particularly limited, and for example, a known coating method such as brush coating, flow coating, dip coating, spray coating, spin coating or the like can be employed.
  • the temperature for drying after coating is preferably 20 to 110 ° C.
  • the ultraviolet irradiation after drying is 50 to 3,000 mJ / cm 2 from the viewpoint of fast curability and workability as the irradiation amount (integrated light amount) of the ultraviolet rays used when the composition of the present invention is cured.
  • the apparatus used for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known thing is mentioned. Heating may be used in combination for curing.
  • the formation method of the said resin layer is a method similar to the composition of this invention, It can form by the process of apply
  • the laminate of the present invention can be used for, for example, an electronic image display device, a spectacle lens, a protective cover for lighting (particularly LED lighting), a solar cell module member, and the like.
  • the electronic image display device include display-use electronic device components such as a personal computer, a television, a touch panel, and a wearable terminal (for example, a computer terminal that can be worn on the body such as a glasses type or a wrist watch type).
  • the laminated body of the present invention can be incorporated in an electronic image display device or the like, or can be retrofitted (for example, attached from the outside).
  • the laminate of the present invention When the laminate of the present invention is built in an electronic image display device or the like, it can be applied to a portion other than the reflector, for example. Specifically, for example, it can be applied to a lens sheet, a diffusion sheet, and a light guide plate.
  • the composition of the present invention can be directly applied to an electronic image display device to form a cured film.
  • Examples 1 to 11 and Comparative Examples 1 to 7 ⁇ Preparation of composition> Each component of the following Table 1 was mixed with the composition (parts by mass) shown in Table 1 using a stirrer to prepare a composition.
  • UV ultraviolet rays
  • UV irradiation condition illumination 300 mW /
  • the composition was cured by cm 2 , an integrated light quantity of 300 mJ / cm 2 , and the UV irradiation device was a high-pressure mercury lamp) to prepare a laminate.
  • ⁇ Bending resistance (winding test)> The PET base material side of the prepared specimen (thickness: 5 ⁇ m, 10 ⁇ m) was wrapped around a circular container, and the diameter of the container in which “cracks” were found in the cured film was measured. As a result, the case where the diameter of the container was less than 10 mm was evaluated as “ ⁇ ” as being excellent in bending resistance, and the case where the diameter of the container was 10 mm or more was evaluated as “x” as being poor in bending resistance. .
  • ⁇ 6.0 indicates that “crack” did not enter the cured film even when a circular container having a diameter of 6.0 mm was used
  • 6.0 indicates that “crack” was found in the cured film when a circular container having a diameter of 6.0 mm was used.
  • (Meth) acrylic block polymer B-1 Clarity LA-2250 (weight average molecular weight: 85000, glass transition temperature of block chain (b1): ⁇ 40 ° C., glass transition temperature of block chain (b2): 105 ° C.
  • Block chain (b2) content 23% by mass, manufactured by Kuraray Co., Ltd.
  • PMMA homopolymer polymethyl methacrylate (Delpet 72, glass transition temperature: 105 ° C., manufactured by Asahi Kasei Chemicals)
  • PMMA-PBA random copolymer: random copolymer of methyl methacrylate (MMA) and butyl acrylate (BA) (PX47-6, MMA / BA 67/33, glass transition temperature: 30 ° C., manufactured by Asia Industries, Ltd. )
  • PBA homopolymer butyl acrylate polymer (weight average molecular weight: 50000, glass transition temperature
  • Photopolymerization initiator C-1 Irgacure 184 (manufactured by BASF)
  • Compound D-1 Compound having a naphthalimide skeleton (R 1 in the above formula (1) is —CH 2 CH (CH 2 CH 2 CH 3 ) 2 , and R 2 is —O—CH 3 .
  • Compound E-1 Compound having a benzotriazole skeleton (Tinuvin Carbo protect, manufactured by BASF) ⁇ Methyl ethyl ketone: solvent ⁇ Anisole: solvent ⁇ Ethyl acetate: solvent ⁇ Cyclohexanone: solvent
  • Example 12 to 15 Using the composition prepared in Example 1, laminate A and laminate B were prepared by the following method, and the adhesion of the cured film was evaluated by the following method.
  • PET film ⁇ Manufacture of laminate A-base material (PET film)> After drying a polyethylene terephthalate film (PET fabric: trade name U46, manufactured by Toray Industries, Inc., thickness 125 ⁇ m) with an acrylic resin composition having the product numbers shown in Table 2 below (both manufactured by Yokohama Rubber Co., Ltd.) using a bar coater. The film was applied with a clearance setting such that the film thickness was 1.5 ⁇ m, dried for 1 minute under the condition of 80 ° C., and then UV (UV) using GS UV SYSTEM manufactured by Kawaguchi Spring Manufacturing Co., Ltd.
  • UV UV
  • UV irradiation conditions illuminance: 300 mW / cm 2 , integrated light quantity: 300 mJ / cm 2 , UV irradiation apparatus: high-pressure mercury lamp
  • a wet pen 8 sets of pen numbers 30, 32, 34, 36, 38, 40, 42, and 44 mN / m, manufactured by Alcotest
  • the time passed the state of the pen streaks was visually confirmed, the largest pen number that did not repel ink was selected, and the surface tension was determined.
  • Example 1 the composition prepared in Example 1 was applied to the acrylic resin layer using a bar coater with a clearance setting such that the film thickness after drying was 1.5 ⁇ m. After drying for a minute, this was irradiated with ultraviolet rays (UV) using a GS UV SYSTEM manufactured by Kawaguchi Spring Mfg. Co., Ltd. (UV irradiation conditions: illuminance 300 mW / cm 2 , integrated light quantity 300 mJ / cm 2 , UV irradiation apparatus was a high-pressure mercury lamp The composition was cured to prepare a laminate.
  • UV ultraviolet rays
  • Laminate B was prepared in the same manner as laminate A except that a cycloolefin film (COP fabric: trade name ZF16-100, manufactured by Nippon Zeon Co., Ltd., thickness 100 ⁇ m) subjected to corona treatment was used as the substrate.
  • COP fabric trade name ZF16-100, manufactured by Nippon Zeon Co., Ltd., thickness 100 ⁇ m
  • ⁇ Adhesion> The produced laminates A and B were subjected to a cross-cut peel test based on JIS K5400 to evaluate the adhesion. Specifically, using a cutter, cut only 1mm pitch in the cured film part and resin layer part of each laminate to make 100 bases (10x10), and cellophane adhesive on the bases A tape (18 mm in width) was completely attached, and immediately pulled off while keeping one end of the tape at a right angle to the substrate, and the number of remaining bases without being completely peeled was examined. When the number of remaining bases was 75 or more, it was evaluated as “ ⁇ ” as being excellent in adhesion, and when it was less than 75, it was evaluated as “x” as being slightly inferior in adhesion. The results are shown in Table 2 below.

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Abstract

La présente invention concerne une composition de résine durcissable par ultraviolets capable de former un film de revêtement durci présentant une excellente dureté ainsi qu'une excellente résistance à la flexion. Cette composition de résine durcissable par ultraviolets contient un composé (A) de (méth)acrylate multifonctionnel comprenant deux groupes (méth)acryloyloxy ou plus dans une molécule, un polymère à blocs (méth)acryliques (B), et un amorceur de photopolymérisation (C), le polymère à blocs (méth)acryliques (B) possédant une chaîne de blocs (b1) présentant une température de transition vitreuse inférieure ou égale à 0 °C et une chaîne de blocs (b2) présentant une température de transition vitreuse supérieure ou égale à 60 °C.
PCT/JP2014/082858 2013-12-27 2014-12-11 Composition de résine durcissable par ultraviolets et stratifié WO2015098549A1 (fr)

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CN106029702A (zh) 2016-10-12
TWI665252B (zh) 2019-07-11

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