WO2016098713A1 - Composition de résine durcissable par rayonnement ultraviolet, et stratifié - Google Patents

Composition de résine durcissable par rayonnement ultraviolet, et stratifié Download PDF

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Publication number
WO2016098713A1
WO2016098713A1 PCT/JP2015/084886 JP2015084886W WO2016098713A1 WO 2016098713 A1 WO2016098713 A1 WO 2016098713A1 JP 2015084886 W JP2015084886 W JP 2015084886W WO 2016098713 A1 WO2016098713 A1 WO 2016098713A1
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Prior art keywords
compound
meth
skeleton
blue light
resin composition
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PCT/JP2015/084886
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English (en)
Japanese (ja)
Inventor
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 JP2016564836A priority Critical patent/JP6229802B2/ja
Priority to CN201580061548.XA priority patent/CN107108819B/zh
Publication of WO2016098713A1 publication Critical patent/WO2016098713A1/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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters

Definitions

  • the present invention relates to an ultraviolet curable resin composition and a laminate having a cured film formed using the same.
  • a light source for example, an LED backlight
  • an electronic image display device that has been widely used in recent years emits light having a wavelength of about 385 to 495 nm, that is, so-called blue light. It has been pointed out that this blue light has adverse effects such as eye strain and dry eye symptoms; decreased retina function; and the secretion of melatonin that promotes sleep. is there.
  • Patent Document 1 describes “an optical article characterized by containing fullerenes as an absorption component of blue light” as an optical filter capable of cutting at least part of visible light of 380 to 500 nm. ([Claim 1] [0009]).
  • Patent Document 2 discloses an “ultraviolet curable resin composition for forming the cured film in a laminate having a film and a cured film on the film and used in an electronic image display device.
  • An ultraviolet curable resin composition comprising the following components (A) to (C), wherein the amount of the component (C) is 0.7 to 2.0% by mass of the nonvolatile component.
  • JP 2007-093927 A Japanese Patent No. 5559446
  • the present inventors have examined the fullerenes described in Patent Document 1, and have found that the blue light cut function is not sufficient.
  • the present inventors have studied the ultraviolet curable resin composition described in Patent Document 2, and it is clear that although it has a good blue light cut function, there is room for further improvement. did.
  • an object of the present invention is to provide an ultraviolet curable resin composition capable of forming a cured film having an excellent blue light cut function and a laminate having a cured film formed using the ultraviolet curable resin composition.
  • the present inventors have found that a compound having a benzoxazoline skeleton and / or a phenyltriazine skeleton as a blue light absorber together with a polyfunctional (meth) acrylate compound and a photopolymerization initiator.
  • the present invention was completed by finding that a cured film formed using an ultraviolet curable resin composition containing a compound having excellent blue light cut function. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • the blue light absorbent (C) includes a compound (C1) having a benzoxazoline skeleton and / or a compound (C2) having a phenyltriazine skeleton,
  • An ultraviolet curable resin composition for forming a cured film that reduces the transmittance of at least part of light in the wavelength region of 385 nm to 495 nm.
  • 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 blue light absorbent (C) includes at least the compound (C1) having the benzoxazoline skeleton, and the compound (C1) having the benzoxazoline skeleton is a compound represented by the following formula (1).
  • the ultraviolet curable resin composition according to any one of [1] to [3]. (In Formula (1), R 1 represents a hydrogen atom or an organic group, and a plurality of R 1 may be the same or different.)
  • the blue light absorbent (C) includes at least the compound (C2) having the phenyltriazine skeleton, and the compound (C2) having the phenyltriazine skeleton is a compound represented by the following formula (2).
  • the blue light absorbent (C) is further selected from the group consisting of a compound (C3) having a naphthalimide skeleton, a compound (C4) having a perylene skeleton, and a compound (C5) having a benzotriazole skeleton.
  • the ultraviolet curable resin composition according to any one of [1] to [5], comprising at least one kind of compound.
  • a resin layer is further provided between the substrate and the cured film, The laminate according to [7], wherein the resin layer is an acrylic resin layer having a surface tension of 32 mN / m or more.
  • the laminated body which has an ultraviolet curable resin composition which can form the cured film excellent in a blue light cut function, and a cured film formed using this can be provided. Moreover, since the laminated body of this invention has a cured film formed using the ultraviolet curable resin composition of this invention, it is excellent in a blue light cut function.
  • 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 photopolymerization initiator (B), and a blue light absorber (C), and the blue light absorber (C) has a compound (C1) having a benzoxazoline skeleton and / or a phenyl triazine skeleton.
  • An ultraviolet curable resin composition for forming a cured film containing a compound (C2) for reducing light transmittance of at least part of a wavelength region of 385 nm to 495 nm.
  • (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 ultraviolet curable resin composition containing the compound (C2) having a phenyltriazine skeleton the formed cured film has a blue light cut function.
  • a polyfunctional (meth) acrylate compound (A), a photoinitiator (B), a blue light absorber (C), and another arbitrary component are explained in full detail.
  • 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) is the reason why the coating property of the composition of the present invention is improved and the hardness of the cured film is improved. Therefore, 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 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 (B) described later can be performed.
  • a compound represented by the following formula (Ia) 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 formula (Ia) include the following compounds.
  • the compound represented by the following formula (Ib) and the compound represented by the following formula (Ic) are preferable.
  • 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 (Ia) is more favorable.
  • the compound represented by (IIa) is preferred.
  • m represents an integer of 2 to 5
  • chiral agent (A3) other than the compound represented by the formula (IIa) specifically, for example, a compound represented by the following formula (IIb) and a compound represented by the following formula (IIc) are preferable. It is mentioned in.
  • Examples of the chiral agent (A3) other than the compounds represented by the above formulas (IIa) to (IIc) 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 photopolymerization initiator (B) 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 (B) 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 (B) 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.
  • the composition of the present invention contains at least the compound (C1) having a benzoxazoline skeleton and / or the compound (C2) having a phenyltriazine skeleton as the blue light absorbent (C).
  • the composition of the present invention has a blue light-absorbing function as a whole, and therefore, as a blue light absorbent (C), a compound (C3) having a naphthalimide skeleton, a compound having a perylene skeleton ( It is preferable to contain at least one compound selected from the group consisting of C4) and a compound (C5) having a benzotriazole skeleton.
  • the compound (C1) having the benzoxazoline skeleton is not particularly limited as long as it is a compound having a benzoxazole ring.
  • the compound (C1) having the benzoxazoline skeleton is preferably a compound represented by the following formula (1) because the blue light cut function is better as a whole.
  • the compound represented by the formula (1a) is more preferable.
  • R 1 represents a hydrogen atom or an organic group, and a plurality of R 1 may be the same or different.
  • Examples of the organic group represented by R 1 in the above formula (1) include a hydrocarbon group which may have a hetero atom, and specifically include, for example, an aliphatic hydrocarbon group, an alicyclic ring. Formula hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof may be mentioned and may have an unsaturated bond. Further, the hydrocarbon group represented by R 1 is preferably a linear or branched alkyl group, and more preferably a branched alkyl group. In addition, the hydrocarbon group represented by R 1 preferably has 1 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
  • Examples of commercially available compounds (C1) having such a benzoxazoline skeleton include Tinopearl OBOCO (manufactured by BASF), Nikka Flow OB (manufactured by Nippon Chemical Industry Co., Ltd.), and the like.
  • the content of the compound (C1) having the benzoxazoline skeleton does not include the compound (C2) having a phenyltriazine skeleton described later, 100 parts by mass of the polyfunctional (meth) acrylate compound (A)
  • the amount is preferably 0.1 to 1.0 part by mass, more preferably 0.3 to 0.5 part by mass.
  • the total content thereof is determined by the polyfunctional (meth) acrylate compound (A) 100.
  • the amount is preferably 0.1 to 1.0 part by weight, more preferably 0.3 to 0.5 part by weight with respect to part by weight.
  • the compound (C2) having the phenyltriazine skeleton is not particularly limited as long as it has a benzene ring (phenyl group) and a triazine ring and these are bonded by a single bond.
  • the compound (C2) having the phenyltriazine skeleton is preferably a compound represented by the following formula (2) because the blue light cut function is better as a whole.
  • a compound represented by formula (2a) is more preferable.
  • R 2 represents a hydrogen atom or an organic group
  • R 3 represents a hydrogen atom or an organic group
  • a plurality of R 2 may be the same or different
  • a plurality of R 3 may be the same or different.
  • Examples of the organic group represented by R 2 and R 3 in the above formula (2) include a hydrocarbon group which may have a hetero atom, specifically, for example, an aliphatic hydrocarbon group. , An alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof, which may have an unsaturated bond.
  • the hydrocarbon groups represented by R 2 and R 3 are preferably each independently a linear or branched alkyl group, and more preferably a linear alkyl group.
  • the number of carbon atoms of the hydrocarbon group represented by R 2 and R 3 is preferably 1 to 12, and more preferably 1 to 6.
  • Examples of commercially available compounds having such a phenyltriazine skeleton (C2) include, for example, Tinuvin 400 (manufactured by BASF), Tinuvin 405 (manufactured by BASF), Tinuvin 460 (manufactured by BASF), Tinuvin 477 (manufactured by BASF) ), Tinuvin rice cake 479 (manufactured by BASF) and the like.
  • the content of the compound (C2) having the phenyltriazine skeleton does not include the compound (C1) having the benzoxazoline skeleton described above, 100 parts by mass of the polyfunctional (meth) acrylate compound (A) The amount is preferably 0.1 to 1.0 part by mass, more preferably 0.3 to 0.5 part by mass.
  • 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 is better.
  • the compound (C3) having a phthalimide skeleton is preferably contained.
  • R 4 represents a hydrogen atom or an organic group
  • R 5 represents a hydrogen atom or an organic group
  • a plurality of R 5 may be the same or different.
  • Examples of the organic group represented by R 4 and R 5 in the above formula (3) include a hydrocarbon group which may have a hetero atom, specifically, for example, an aliphatic hydrocarbon group. , An alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof, which may have an unsaturated bond. Further, the hydrocarbon group represented by R 4 is preferably a linear or branched alkyl group, and preferably has 1 to 12 carbon atoms.
  • the hydrocarbon group represented by R 5 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
  • the content is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound (A).
  • the amount is more preferably 0.5 to 2.0 parts by mass.
  • the composition of the present invention can absorb a long wavelength side region (420 to 495 nm) in the blue light region, and the blue light cut function as a whole is better, so that the perylene represented by the following formula (4) is used.
  • the compound (C4) having a skeleton is preferably contained.
  • R 6 represents a hydrogen atom or an organic group
  • R 7 represents a hydrogen atom or an organic group
  • a plurality of R 6 may be the same or different
  • a plurality of R 6 7 may be the same or different.
  • Examples of the organic group represented by R 6 and R 7 in the above formula (4) include a hydrocarbon group which may have a hetero atom, specifically, for example, an aliphatic hydrocarbon group. , An alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof, which may have an unsaturated bond.
  • Examples of the commercially available compound (C4) having a perylene skeleton include Lumogen F Yellow 083 (manufactured by BASF).
  • the content is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound (A). 0.5 to 2.0 parts by mass is more preferable.
  • composition of the present invention can absorb a low wavelength region (385 to 430 nm) in the blue light region, and the compound having a benzotriazole skeleton (C5) can be obtained because the blue light cut function is better overall. It is preferable to contain.
  • Examples of the compound (C5) having a benzotriazole skeleton include compounds represented by the following formula (5).
  • R 8 represents a hydrogen atom or an organic group.
  • Examples of the organic group represented by R 8 in the above formula (5) include a hydrocarbon group which may have a hetero atom, specifically, for example, an aliphatic hydrocarbon group, an alicyclic ring.
  • Formula hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof may be mentioned and may have an unsaturated bond.
  • Examples of commercially available compounds (C5) having such a benzotriazole skeleton include Tinuvin Carbo protect (manufactured by BASF) and Tinuvin 38384 (manufactured by BASF).
  • the content of the compound (C5) having the benzotriazole skeleton is 0.1 to 1.0 part by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound (A).
  • the amount is 0.3 to 0.5 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.
  • the 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.
  • Additives such as foaming agents, matting agents, light stabilizers, dyes, pigments can be further contained.
  • a filler it is more preferable to contain silica from the viewpoint of easy slipping.
  • Silica is not particularly limited, and examples thereof include wet silica, dry silica, fumed silica, and diatomaceous earth. Among these, fumed silica is preferably contained from the viewpoint of excellent transparency.
  • composition of the present invention is not particularly limited, and the above-mentioned polyfunctional (meth) acrylate compound (A), photopolymerization initiator (B) and blue light absorbent (C), solvent, leveling agent and additive Can be manufactured by uniformly mixing.
  • 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 laminate of the present invention preferably has a resin layer between the substrate and the cured film for the reason that the adhesion between the cured film and the substrate is good.
  • 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, surfactant, hydrophilicity or lipophilicity imparting 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 polyfunctional (meth) acrylate (a) is not particularly limited as long as it is a compound having two or more (meth) acryloyloxy groups.
  • the (meth) acryloyloxy group can be bonded to an organic group.
  • the hydrocarbon group which may have hetero atoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom, is mentioned, for example.
  • Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof.
  • the hydrocarbon group may include a straight chain and a branched chain, and may have an unsaturated bond.
  • the polyfunctional (meth) acrylate (a) has a high hardness of the resulting acrylic resin layer, and has better adhesion between the substrate and the cured film. It is preferable to have twelve.
  • polyfunctional (meth) acrylate (a) examples include polyhydric alcohol (meth) acrylic acid esters and urethane (meth) acrylates.
  • 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 he
  • urethane (meth) acrylates examples include (meth) acrylic acid esters of polyhydric alcohols (in this case, (meth) acrylic acid esters of polyhydric alcohols include those having at least one hydroxy group). ) And a polyisocyanate compound.
  • (meth) acrylic acid ester of polyhydric alcohol used when producing urethane (meth) acrylate examples include the same as those described above.
  • polyisocyanate compounds used in the production of urethane (meth) acrylate include tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and tolidine diisocyanate.
  • Aromatic polyisocyanates such as 1,5-naphthalene diisocyanate and triphenylmethane triisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis (Isocyanate methyl) Cyclohexane, (including linear and / or cycloaliphatic systems.) Aliphatic polyisocyanates such as dicyclohexylmethane diisocyanate; these isocyanurate, biuret body, an adduct; and the urethane prepolymer.
  • 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.
  • the same thing as an initiator (B) can be selected suitably, and can be used.
  • the hard coat resin composition is within a range that does not impair the object of the present invention.
  • additives such as an antifoaming agent, a leveling agent, a matting agent, a light stabilizer, a dye and a pigment can be further contained.
  • 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 is not particularly limited, but is preferably about 0.01 to 50 ⁇ m, more preferably 1 to 5 ⁇ 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 with 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 and 2 ⁇ 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. ⁇ Manufacture of laminates> Each composition obtained as described above was formed into a polyethylene terephthalate film (PET fabric, trade name: Lumirror U-403, thickness: 125 ⁇ m, manufactured by Toray Industries, Inc.) using a bar coater and a film thickness after drying of 5 ⁇ m. This was applied with a clearance setting, and this was dried at 80 ° C.
  • PET fabric trade name: Lumirror U-403
  • thickness 125 ⁇ m, manufactured by Toray Industries, Inc.
  • UV irradiation condition illuminance
  • the composition was cured by 300 mW / cm 2 , the integrated light quantity 300 mJ / cm 2 , and the UV irradiation device was a high-pressure mercury lamp) to prepare a laminate.
  • Photopolymerization initiator B-1 Irgacure 184 (manufactured by BASF) Fumed silica: Aerosil R972 (Nippon Aerosil) Leveling agent: Nonionic fluorosurfactant (trade name FTX-218 dispersion, manufactured by Neos)
  • the composition prepared by blending the compound (C1) having a benzoxazoline skeleton and / or the compound (C2) having a phenyl triazine skeleton has an average blue light cut rate.
  • the pencil hardness and the adhesion were good (Examples 1 to 11).
  • Example 1 From the comparison between Example 1 and Example 9, as a polyfunctional (meth) acrylate compound (A), a nematic liquid crystalline compound (A2) having two or more (meth) acryloyloxy groups in one molecule, It was also found that the average cut rate of blue light is greatly improved by blending the chiral agent (A3) having two or more (meth) acryloyloxy groups in one molecule.

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne le problème consistant à produire : une composition de résine durcissable par rayonnement ultraviolet apte à former un film de revêtement durci ayant une excellente fonction d'absorption de la lumière bleue ; et un stratifié ayant un film de revêtement durci formé en utilisant la composition. Cette composition de résine durcissable par rayonnement ultraviolet sert à former un film de revêtement durci qui réduit la transmittance d'au moins une partie de la lumière dans la zone de longueurs d'ondes de 385 à 495 nm, et qui contient un composé (méth)acrylate polyfonctionnel (A) ayant deux groupes (méth)acryloyloxy ou plus par molécule, un initiateur de photopolymérisation (B), et un agent d'absorption de la lumière bleue (C). L'agent d'absorption de la lumière bleue (C) comprend un composé (C1) ayant un squelette benzoxazoline et/ou un composé (C2) ayant un squelette phényltriazine.
PCT/JP2015/084886 2014-12-16 2015-12-14 Composition de résine durcissable par rayonnement ultraviolet, et stratifié WO2016098713A1 (fr)

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WO2018180929A1 (fr) * 2017-03-31 2018-10-04 富士フイルム株式会社 Corps moulé en résine et corps stratifié découpé à la lumière bleue

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CN107108819A (zh) 2017-08-29
CN107108819B (zh) 2020-04-21

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