WO2017195598A1 - 紫外線硬化型樹脂組成物、硬化皮膜、及び、積層体 - Google Patents

紫外線硬化型樹脂組成物、硬化皮膜、及び、積層体 Download PDF

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WO2017195598A1
WO2017195598A1 PCT/JP2017/016498 JP2017016498W WO2017195598A1 WO 2017195598 A1 WO2017195598 A1 WO 2017195598A1 JP 2017016498 W JP2017016498 W JP 2017016498W WO 2017195598 A1 WO2017195598 A1 WO 2017195598A1
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group
meth
polyfunctional
ultraviolet curable
resin composition
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PCT/JP2017/016498
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English (en)
French (fr)
Japanese (ja)
Inventor
依慶 米山
裕一 松木
護 鶴田
丈章 齋木
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横浜ゴム株式会社
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Priority to JP2018516934A priority Critical patent/JPWO2017195598A1/ja
Priority to CN201780025456.5A priority patent/CN109071694A/zh
Publication of WO2017195598A1 publication Critical patent/WO2017195598A1/ja

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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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • 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
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

Definitions

  • the present invention relates to an ultraviolet curable resin composition, a cured film, and a laminate.
  • an ultraviolet curable resin composition for forming such a hard coat layer or hard coat film for example, in the example of Patent Document 1, dipentaerythritol hexaacrylate as a polyfunctional (meth) acrylate and a leveling agent
  • a composition containing 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator and MIBK-ST (wet silica, manufactured by Nissan Chemical Industries, Ltd.) as silica nanoparticles is disclosed.
  • the present invention provides an ultraviolet curable resin composition capable of forming a cured film excellent in recoatability, a cured film formed from the ultraviolet curable resin composition, a substrate, and the above It aims at providing a laminated body provided with a cured film.
  • the present inventors have found that the above problems can be solved by using a specific nonionic oligomer and dry silica together, and have reached the present invention. That is, the present inventor has found that the above problem can be solved by the following configuration.
  • the polyfunctional (meth) acryloyloxy group-containing compound includes the polyfunctional (meth) acryloyloxy group-containing compound having a partial structure represented by the following general formula (A). UV curable resin composition. * -CH 2 CH 2 O- * (A) In formula (A), * represents a bonding position.
  • the content of the nonionic oligomer is 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acryloyloxy group-containing compound.
  • the content of the photopolymerization initiator is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acryloyloxy group-containing compound
  • Mold resin composition. (9) A cured film formed from the ultraviolet curable resin composition according to any one of (1) to (8) above.
  • (10) A laminate comprising a substrate and the cured film according to (9) above. (11) The laminate according to (10), which is a functional film constituting an electronic device component.
  • an ultraviolet curable resin composition capable of forming a cured film excellent in recoatability, a cured film formed from the ultraviolet curable resin composition, a substrate, and the above A laminated body provided with a cured film can be provided.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • (meth) acryloyloxy group means an acryloyloxy group (CH 2 ⁇ CHCOO—) and / or a methacryloyloxy group (CH 2 ⁇ C (CH 3 ) COO—).
  • Acryloyl group means an acryloyl group (CH 2 ⁇ CHCO—) and / or a methacryloyl group (CH 2 ⁇ C (CH 3 ) CO—), and “(meth) acrylate” means acrylate and And / or methacrylate, and “(meth) acryl” means acryl and / or methacryl.
  • the ultraviolet curable resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) comprises a polyfunctional (meth) acryloyloxy group-containing compound, a fluorine atom-containing group, a hydrophilic group, and a lipophilic group.
  • the nonionic oligomer (hereinafter also referred to as “specific nonionic oligomer”), a photopolymerization initiator, and dry silica having an average primary particle size of 100 nm or less. Since the composition of this invention takes such a structure, it is thought that the effect mentioned above is acquired. The reason is not clear, but it is presumed that it is as follows.
  • the composition of the present invention contains a specific nonionic oligomer. Therefore, when a coating film is formed using the composition of the present invention, it is considered that the specific nonionic oligomer tends to be unevenly distributed on the surface of the coating film due to the action of the fluorine atom-containing group. As a result, it is speculated that the hydrophilic group of the specific nonionic oligomer increases the wettability of the surface of the coating film and improves the recoatability.
  • the specific nonionic oligomer since the specific nonionic oligomer also has a lipophilic group, it has high affinity with other components (for example, a polyfunctional (meth) acryloyloxy group-containing compound), and the uneven distribution of the specific nonionic oligomer described above is It is considered that the surface becomes uniform and recoatability is ensured.
  • the composition of the present invention contains silica, since the contained silica is fine dry silica, it has a high affinity with the above-described lipophilic group and prevents the uneven distribution of the above-described specific nonionic oligomer. It is thought that there is no.
  • the polyfunctional (meth) acryloyloxy group-containing compound 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.
  • the number of (meth) acryloyloxy groups contained in the polyfunctional (meth) acryloyloxy group-containing compound is preferably 3 or more from the viewpoint of excellent coating properties and curability of the composition of the present invention. Is more preferable.
  • the polyfunctional (meth) acryloyloxy group-containing compound is preferably a compound other than the specific nonionic oligomer described later because the effect of the present invention is more excellent.
  • the polyfunctional (meth) acryloyloxy group-containing compound is a group consisting of a polyfunctional (meth) acryloyloxy group-containing compound having a (meth) acrylic acid ester of a polyhydric alcohol and a urethane group because the effects of the present invention are more excellent. It is preferable to include at least one polyfunctional (meth) acryloyloxy group-containing compound selected more preferably, and it is more preferable to include a polyfunctional (meth) acryloyloxy group-containing compound having a urethane group.
  • 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
  • the ratio of the polyfunctional alcohol (meth) acrylic acid ester in the polyfunctional (meth) acryloyloxy group-containing compound is The content is preferably 5 to 95% by mass, and more preferably 30 to 80% by mass.
  • polyfunctional (meth) acryloyloxy group-containing compound having a urethane group examples include a reaction product of a polyhydric alcohol (meth) acrylic acid ester and a polyisocyanate compound.
  • the (meth) acrylic acid ester of a polyhydric alcohol used when producing a polyfunctional (meth) acryloyloxy group-containing compound having a urethane group for example, the polyhydric alcohol (meth) described above is used.
  • acrylic esters those having at least one hydroxy group can be mentioned.
  • Examples of the polyisocyanate compound used for producing a polyfunctional (meth) acryloyloxy group-containing compound having a urethane group include tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, and xylylene.
  • Aromatic polyisocyanates such as diisocyanate, tetramethylxylylene diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane 1,4-diisocyanate, isophorone diisocyanate , Bis (isocyanatomethyl) cyclohexane, aliphatic polyisocyanates such as dicyclohexylmethane diisocyanate; these isocyanurate, biuret body, an adduct; and the like are.
  • the polyfunctional (meth) acryloyloxy group-containing compound contains a polyfunctional (meth) acryloyloxy group-containing compound having a urethane group
  • the polyfunctional (meth) having a urethane group in the polyfunctional (meth) acryloyloxy group-containing compound The proportion of the acryloyloxy group-containing compound is preferably 5 to 95% by mass, and more preferably 20 to 80% by mass.
  • a suitable aspect of the polyfunctional (meth) acryloyloxy group-containing compound for example, a compound having two or more (meth) acryloyloxy groups and a partial structure represented by the following general formula (A) (hereinafter, Also referred to as “compound A”).
  • compound A a compound having two or more (meth) acryloyloxy groups and a partial structure represented by the following general formula (A) (hereinafter, Also referred to as “compound A”).
  • Compound A preferably has a group represented by the following general formula (a).
  • L represents a single bond or * 1- (COC 5 H 10 O) m- * 2 (where m represents an integer of 1 or more (preferably an integer of 1 to 8)).
  • * 1 represents a bonding position with an oxygen atom
  • * 2 represents a bonding position with X).
  • X represents a (meth) acryloyl group.
  • n represents an integer of 1 or more (preferably an integer of 1 to 10).
  • Compound A is preferably a compound represented by the following formula (N).
  • R 1 to R 3 each independently represents a group represented by the following a, b or c. However, at most one of R 1 to R 3 is represented by a. a: —H or — (CH 2 ) n —OH (where n represents an integer of 1 to 10 (preferably an integer of 2 to 6)) b: — (CH 2 ) n —O— (COC 5 H 10 O) m —R (where R represents a (meth) acryloyl group, n represents 2 and m represents an integer of 1 or more (preferably Represents an integer of 1 to 8)) c: — (CH 2 ) n —O—R (where R represents a (meth) acryloyl group and n represents 2)
  • NK ester A-9300 ⁇ -caprolactone modified tris- (acryloxyethyl) isocyanate manufactured by Shin-Nakamura Chemical Co., Ltd., which is ethoxylated isocyanuric acid triacrylate.
  • examples thereof include, but are not limited to, NK ester A-9300 1CL manufactured by Shin-Nakamura Chemical Co., Ltd. and Aronix M-327 manufactured by Toagosei Co., Ltd.
  • the proportion of compound A in the polyfunctional (meth) acryloyloxy group-containing compound is preferably 1 to 90% by mass, and preferably 5 to 70% by mass. It is more preferable that
  • the polyfunctional (meth) acryloyloxy group-containing compound contained in the composition of the present invention is one kind of polyfunctional (meth) acryloyloxy group-containing compound, two or more kinds of polyfunctional (meth) acryloyloxy A group-containing compound may be included.
  • the polyfunctional (meth) acryloyloxy group-containing compound preferably contains the compound A described above for the reason that the effects of the present invention are more excellent, and is a polyfunctional (meth) acrylic acid ester of polyhydric alcohol and a polyfunctional compound having a urethane group ( It is more preferable to include all of the (meth) acryloyloxy group-containing compound and compound A.
  • Nonionic oligomer (specific nonionic oligomer) containing a fluorine atom-containing group, a hydrophilic group and a lipophilic group contained in the composition of the present invention comprises a fluorine atom-containing group, a hydrophilic group and a lipophilic group. If it is a nonionic oligomer to contain, it will not restrict
  • nonionicity means nonionicity.
  • the oligomer means a polymer having a number average molecular weight of several hundred to several tens of thousands (preferably 500 to 50,000).
  • the number average molecular weight in this specification be the polystyrene conversion value measured by the gel permeation chromatography (GPC) method.
  • the skeleton (main chain) of the nonionic oligomer is preferably polyoxyethylene ether or (meth) acrylic, more preferably (meth) acrylic, because the effect of the present invention is more excellent. preferable.
  • a fluorine atom containing group, a hydrophilic group, and a lipophilic group are explained in full detail first, and a suitable aspect is explained in full detail after that.
  • the fluorine atom-containing group is not particularly limited as long as it is a group containing a fluorine atom, but is preferably a hydrocarbon group in which at least some of the hydrogen atoms are substituted with fluorine atoms. It may be a hydrocarbon group in which all hydrogen atoms are substituted with fluorine atoms (perfluorohydrocarbon group). Although it does not restrict
  • the aliphatic hydrocarbon group may be linear, branched or cyclic, but is preferably branched.
  • aliphatic hydrocarbon group examples include linear or branched alkyl groups (particularly 1 to 50 carbon atoms), linear or branched alkenyl groups (particularly 2 to 50 carbon atoms), Examples thereof include linear or branched alkynyl groups (particularly those having 2 to 50 carbon atoms).
  • aromatic hydrocarbon group examples include an aryl group and a naphthyl group.
  • aryl group examples include aryl groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group.
  • the fluorine atom-containing group is preferably a branched aliphatic hydrocarbon group (branched fluoroaliphatic hydrocarbon group) in which at least some of the hydrogen atoms are substituted with fluorine atoms.
  • the branched fluoroaliphatic hydrocarbon group is preferably composed of an alkyl group and / or alkenyl group having a branched structure, and at least some of the hydrogen atoms are preferably substituted with fluorine atoms.
  • fluoroaliphatic hydrocarbon group examples include perfluoroisopropyl, perfluoroisobutyl, perfluoro s-butyl, perfluoro t-butyl, perfluoroisopentyl, perfluoroneopentyl, perfluorot-pentyl, perfluoroiso Perfluoro C 3-16 alkyl groups such as hexyl and perfluoro-2-ethylhexyl groups, or perfluoro C 3-16 alkenyl groups corresponding to these alkyl groups (for example, perfluoroneopentan-1-yl group, perfluoro A neopentan-2-yl group, a perfluoro t-pentan-1-yl group, a perfluoro t-pentan-2-yl group, etc.).
  • the aliphatic hydrocarbon group preferably has a highly branched structure, and 2 to 6 (preferably 2 to 4) alkyl groups may be branched based on the longest carbon chain.
  • the alkyl chain may be a methyl group, and in the case of an alkyl chain having 2 or more carbon atoms (for example, a C 2-4 alkyl group), it may be a straight chain or branched like an isopropyl group. Also good.
  • Such highly branched hydrocarbon groups include, for example, dimers (dimers) and trimers of alkenes (C 3-6 alkenes such as propylene, butene, isobutene, pentene, and isopentene, especially branched alkenes). In many cases, it corresponds to a hydrocarbon group of a multimer (preferably dimer to tetramer, particularly trimer) such as (trimer) and tetramer (tetramer).
  • alkyl group and / or alkenyl group corresponding to the fluoroalkyl group and / or fluoroalkenyl group having such a branched structure examples include a 1,3-dimethylbutyl group and a 1,3-dimethyl-2-isopropylbutyl group.
  • Branched chain C 6-18 alkyl groups such as 2-ethyl-2-butyl-hexyl group, 2,2,4-trimethylpentyl group, 2,2,4-trimethyl-2-isobutylpentyl group; Corresponding groups (1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-buten-1-yl group), groups corresponding to propylene trimer (1,3-dimethyl-2-isopropylidenebutenyl Group, 1,3-dimethyl-2-isopropyl-1-butenyl group), group corresponding to butene trimer (2-ethyl-2-butyl-1-hexene) -1-yl group, 2-ethyl-2-butyl-2-hexene-1-group), groups corresponding to isobutene dimer (2,2,4-trimethyl-1-penten-1-yl group, 2, 2,4-trimethyl-2-penten-1-yl group), groups corresponding to isobuten
  • the aliphatic hydrocarbon group having a branched structure may be a perfluoroaliphatic hydrocarbon group in which at least a part of hydrogen atoms are substituted with fluorine atoms, and all the hydrogen atoms are substituted with fluorine atoms. Also good.
  • the branched fluoroalkyl group and / or branched fluoroalkenyl group often contains at least one fluoro-branched alkyl group and / or fluoro-branched alkenyl group as the minimum branched chain unit.
  • Examples thereof include perfluoro C 3-6 alkyl groups such as perfluoroisopropyl group, perfluoroisobutyl group and perfluoroisopentyl group.
  • Examples of the fluoro-branched alkenyl group include perfluoroisopropylidene group, perfluoro
  • perfluoro C 3-6 alkenyl groups such as a 1-isobutenyl group and a perfluoro-1-isopentenyl group.
  • the smallest branched chain unit often contains at least one or both of a perfluoro C 3-6 alkyl group and a perfluoro C 3-6 alkenyl group.
  • fluoroaliphatic hydrocarbon group for example, a group represented by the following formula (2a) or (2b) may be mentioned.
  • the hydrophilic group is not particularly limited as long as it is a hydrophilic group, but it is more preferably a hydroxy group. In addition, it is preferable that a hydrophilic group does not contain a fluorine atom.
  • the lipophilic group is not particularly limited as long as it is a lipophilic group, but a hydrocarbon group is more preferable because the effect of the present invention is more excellent.
  • Another preferred embodiment of the lipophilic group includes a polyoxyalkylene ether skeleton (for example, a polypropylene glycol (PPG) skeleton, a polyethylene glycol (PEG) skeleton), and the like.
  • the lipophilic group is preferably a group that does not contain a fluorine atom or a group that does not contain a hydroxy group.
  • hydrocarbon group are the same as the hydrocarbon groups described for the fluorine atom-containing group.
  • a linear or branched alkyl group is preferable because the effects of the present invention are more excellent.
  • the specific nonionic oligomer preferably has a (meth) acryloyloxy group because the formed cured film is excellent in transparency.
  • the specific nonionic oligomer preferably has a repeating unit having a fluorine atom-containing group, a repeating unit having a hydrophilic group, and a repeating unit having a lipophilic group, because the effects of the present invention are more excellent. It is more preferable to have a repeating unit having a (meth) acryloyloxy group.
  • the repeating unit is preferably a (meth) acrylate type.
  • a monomer which becomes a repeating unit having a fluorine atom-containing group for example, a monomer represented by the following formula (F) is preferable.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a divalent linking group.
  • the divalent linking group include a divalent aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 8 carbon atoms), a divalent aromatic hydrocarbon group (for example, an arylene group, preferably carbon 6-12), —O—, —S—, —SO 2 —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or these (For example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like).
  • R 3 represents the fluorine atom-containing group described above. Specific examples and preferred embodiments of R 3 are as described above.
  • Examples of the monomer that is a repeating unit having a hydrophilic group include hydroxy C 2-10 such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
  • Hydroxyalkyl (meth) acrylates such as alkyl (meth) acrylate; polyoxy C 2-4 alkylene glycol mono (meta) such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate ) Acrylate and the like.
  • Examples of the monomer that becomes a repeating unit having a lipophilic group include C 1-20 alkyl (meth) acrylate; C 5-10 cycloalkyl (meth) acrylate; adamantyl (meth) acrylate, and isobornyl (meth) acrylate.
  • (Meth) acrylates having a bridged cyclic hydrocarbon group aryl (meth) acrylates such as phenyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate, Examples thereof include polyoxy C 2-4 alkylene glycol mono C 1-4 alkyl ether mono (meth) acrylate.
  • R 1 and R 2 each independently represents a hydrogen atom or a methyl group.
  • L represents a divalent linking group. Specific examples and preferred embodiments of L are the same as R 2 in the above formula (F).
  • the ratio of the repeating unit having a fluorine atom-containing group is not particularly limited, but is preferably 5 to 75% by mass, more preferably 10 to 60% by mass, It is more preferably 15 to 50% by mass (particularly 20 to 40% by mass), and particularly preferably 10 to 50% by mass (particularly 25 to 35% by mass).
  • the ratio of the repeating unit having a hydrophilic group is not particularly limited, but is preferably 5 to 50% by mass (particularly 7.5 to 40% by mass), and more preferably 10 to 30% by mass.
  • the proportion of the repeating unit having a lipophilic group is preferably 5 to 70% by mass (particularly 5 to 60% by mass), more preferably 10 to 55% by mass, and 20 to 50% by mass. Is more preferable.
  • a nonionic oligomer represented by the following formula (1) is preferable because the effect of the present invention is more excellent.
  • Rf represents the fluorine atom containing group mentioned above. Specific examples and preferred embodiments of Rf are as described above.
  • R 1 is a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (optionally having a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group) .
  • R 2 is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms (optionally having a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group. .)
  • a plurality of R 2 may be the same or different.
  • R 3 is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (which may optionally have an ether bond).
  • R 4 represents a hydrogen atom or a methyl group.
  • R 5 is a monovalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (preferably 5 to 20 carbon atoms) (optionally halogen atom, ether bond, ester bond, amide bond or An aryl group) or an aryl group.
  • R 6 , R 7 and R 8 are each independently a hydrogen atom or a methyl group. A plurality of R 7 may be the same or different.
  • each of n, m and q is an integer of 1 to 30, and p is an integer of 0 to 30.
  • x is an integer of 1 or 2.
  • the number average molecular weight of the specific nonionic oligomer is preferably 500 to 50,000, more preferably 1000 to 30,000, and further preferably 2,000 to 20,000.
  • the specific nonionic oligomer include Neogene's Footage 710FL, Footage 602A, and Footgent 681.
  • the tergent 710FL is an embodiment having no (meth) acryloyloxy group
  • the tergent 602A and the tergent 681 are embodiments having a (meth) acryloyloxy group.
  • the content of the specific nonionic oligomer is not particularly limited, but may be 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acryloyloxy group-containing compound described above.
  • the amount is preferably 0.1 to 3 parts by mass.
  • the specific nonionic oligomer contained in the composition of the present invention may be one type or two or more types.
  • the photopolymerization initiator contained in the composition of the present invention is not particularly limited as long as it can polymerize the polyfunctional (meth) acryloyloxy group-containing compound by light.
  • Examples of the photopolymerization initiator include alkylphenone compounds, 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
  • the photopolymerization initiator is an ⁇ -hydroxyalkylphenone compound (preferably an ⁇ -hydroxyacetophenone compound) from the viewpoints of light stability, high efficiency of photocleavage, surface curability, compatibility, low volatility, low odor and the like. Compound) and ⁇ -aminoalkylphenone compounds.
  • ⁇ -hydroxyalkylphenone compounds include 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Irgacure 1173 manufactured by BASF).
  • the content of the photopolymerization initiator is not particularly limited, but is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acryloyloxy group-containing compound described above. preferable.
  • the photoinitiator contained in the composition of this invention may be 1 type, or may be 2 or more types.
  • the dry silica contained in the composition of the present invention is not particularly limited as long as it is silica produced or melted in the gas phase.
  • the dry silica may be subjected to a surface treatment. More specifically, examples of the dry silica include silicon halides such as monochlorosilane, dichlorosilane, trichlorosilane, and tetrachlorosilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexa
  • a silicon-containing compound such as siloxanes such as methyldisiloxane and octamethyltrisiloxane and a flammable gas such as oxygen (if necessary, a diluent gas such as nitrogen or an auxiliary combustion gas such as hydrogen is used.
  • Silica produced by a method of burning while jetting from a burner silica produced by a method of heat-treating metallic silicon powder in a flame or other high temperature and oxidizing atmosphere; crushed quartz or silica By melting the agglomerates in a flame and then re-solidifying them Silica produced, and silica, etc.
  • silica produced by a method of burning while jetting from a burner
  • silica produced by a method of heat-treating metallic silicon powder in a flame or other high temperature and oxidizing atmosphere
  • crushed quartz or silica By melting the agglomerates in a flame and then re-solidifying them Silica produced, and silica, etc.
  • dry silica is preferably subjected to surface treatment, and more preferably subjected to hydrophobic treatment.
  • the hydrophobic treatment is intended to be performed with a hydrophobic treatment agent.
  • the silanol group on the dry silica surface reacts with the hydrophobizing surface treatment agent to introduce the hydrophobic group on the dry silica surface.
  • the hydrophobic group is not particularly limited, and examples thereof include an alkyl group, a dimethylsilyl group, a trimethylsilyl group, an alkylsilyl group, and a methacrylsilyl group.
  • the hydrophobizing agent is not particularly limited, and examples thereof include siloxane, silazane, chlorosilane, alkoxysilane, alkylsilane, and silicone oil.
  • examples of the siloxane include octamethylcyclotetrasiloxane.
  • examples of the silazane include hexamethyldisilazane.
  • Examples of the chlorosilane include dimethyldichlorosilane.
  • the alkoxysilane include For example, methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane and the like can be mentioned.
  • alkylsilane examples include octylsilane and the like
  • silicone oil examples include dimethylsilicone oil and methylphenylsilicone oil.
  • Chlorophenyl silicone oil methyl hydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, alcohol modified Silicone oil, amino modified silicone oil, epoxy modified silicone oil, epoxy / polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, (meth) modified silicone oil, ⁇ -methylstyrene modified silicone oil Etc.
  • the average primary particle diameter of the dry silica contained in the composition of the present invention is 100 nm or less. Especially, it is preferable that it is 50 nm or less from the reason which the effect of this invention is more excellent. Although a minimum in particular is not restrict
  • an average primary particle diameter shall mean the 50% volume cumulative diameter (D50) measured using the laser diffraction type particle size distribution measuring apparatus.
  • Aerosil® 90 AEROSIL® 130, AEROSIL® 150, AEROSIL® 200, AEROSIL® 300, AEROSIL® 380, AEROSIL® OX50, AEROSIL® EG50, AEROSIL® TT600 manufactured by Nippon Aerosil Co., Ltd.
  • AEROSIL R972, AEROSIL R972V, AEROSIL R972CF, AEROSIL R974, AEROSIL R976, AEROSIL RX200, AEROSIL R104, AEROSILR12 AEROSIL R812S, AEROSIL R816, AEROSIL R7200, AEROSIL R8200, and AEROSIL R9200 are preferred.
  • the content of dry silica is not particularly limited, but is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acryloyloxy group-containing compound described above.
  • the dry silica contained in the composition of the present invention may be one type or two or more types.
  • 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.
  • MEK, cyclohexanone, and MIBK are preferable, and MEK is more preferable from the viewpoint of excellent solubility, drying property, and paintability.
  • a solvent can be used individually or in combination of 2 types or more, respectively.
  • the content of the solvent is not particularly limited, but from the viewpoint of coatability, it is preferably 5 to 85% by mass in the total amount of the composition.
  • composition of this invention may contain other components other than the component mentioned above.
  • Such components include, for example, UV absorbers, fillers, anti-aging agents, antistatic agents, flame retardants, adhesion promoters, dispersants, antioxidants, antifoaming agents, matting agents, and light stabilizers. , Dyes and pigments.
  • the method for preparing the composition of the present invention is not particularly limited, and examples thereof include a method of mixing the above-described components using a stirrer or the like.
  • the cured film of the present invention is not particularly limited as long as it is formed from the above-described composition of the present invention.
  • the method for producing the cured film of the present invention is not particularly limited.
  • the above-described composition of the present invention is applied on a substrate, and a coating film is formed on the substrate by drying as necessary. Examples include a method of curing the obtained coating film by irradiating with ultraviolet rays.
  • the method for applying the composition of the present invention is not particularly limited, and a known method such as brush coating, flow coating, dip coating, spray coating, spin coating or the like can be employed.
  • the temperature for drying the coating film is not particularly limited, but is preferably 20 to 110 ° C.
  • the irradiation amount (integrated light amount) when irradiating with ultraviolet rays is not particularly limited, but is preferably 50 to 3,000 mJ / cm 2 from the viewpoint of fast curability and workability.
  • 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 thickness of the cured film of the present invention is not particularly limited, but is preferably 0.1 to 100 ⁇ m, and more preferably 1 to 5 ⁇ m.
  • the laminated body of this invention will not be restrict
  • the cured film is as described above.
  • the laminated body of this invention may be further equipped with the resin layer (for example, acrylic resin layer) between a base material and a cured film from viewpoints, such as adhesiveness.
  • the method for forming the cured film is as described above.
  • the method for forming the resin layer is the same as the method for producing the cured film described above.
  • the base material used for the laminated body of this invention is demonstrated.
  • 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 cured film and laminate of the present invention can be used for, for example, electronic image display devices, eyeglass lenses, protective covers for lighting (particularly LED lighting), solar cell module members, 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 laminate of the present invention can be built in or attached to an electronic image display device or the like (for example, sticking from outside). 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 or the like to form a cured film.
  • ⁇ Recoatability> (Contact angle) A 10 ⁇ m 3 water droplet was dropped onto the surface of the cured film at a rate of 2 ⁇ m 3 / sec, and the contact angle [°] was measured using a contact angle measuring device (OCA20, manufactured by Data Physics). The results are shown in Table 1. The smaller the contact angle, the better the recoatability. From the viewpoint of recoatability, the contact angle is preferably 72 ° or less.
  • the dyne number (before heating) [dyne / cm] of the surface of the cured film was measured using a dyne pen (wetting reagent). The results are shown in Table 1. The greater the dyne number, the better the recoatability. From the viewpoint of recoatability, the dyne number (before heating) is preferably 32 or more. Further, the obtained laminate was heated (150 ° C. ⁇ 2 hours), and then the dyne number (after heating) [dyne / cm] of the surface of the cured film was measured in the same manner as before heating. The results are shown in Table 1. In Table 1, “ ⁇ 30” indicates that the dyne number is smaller than 30.
  • the detail of each component described in Table 1 is as follows.
  • the specific nonionic oligomers 1 to 3 correspond to the above-mentioned specific nonionic oligomer (nonionic oligomer represented by the above formula (1)), and the comparative nonionic oligomers 1 to 3 are the above-mentioned specific nonionic oligomers. Not applicable.
  • the polyfunctional (meth) acryloyloxy group-containing compounds 1 to 7 correspond to the above-mentioned compound A, of which the polyfunctional (meth) acryloyloxy group
  • the contained compounds 3 to 4 correspond to the compound represented by the above formula (N).
  • Polyfunctional (meth) acryloyloxy group-containing compound 1 Miramer M-600 (dipentaerythritol hexaacrylate, manufactured by Miwon)
  • Polyfunctional (meth) acryloyloxy group-containing compound 4 NK ester A-9300 (ethoxylated isocyanuric acid triacrylate (the following structure), manufactured by Shin-Nakamura Chemical Co., Ltd., average molecular weight Mw: 423, viscosity: 1000 mPa ⁇ s (25 °C))
  • TMPEOTA trimethylolpropane ethoxytriacrylate (the following structure), manufactured by Daicel-Ornesque, average molecular weight Mw: 428, viscosity: 60 mPa ⁇ s (25 ° C.))
  • Polyfunctional (meth) acryloyloxy group-containing compound 6 Light acrylate BP-4EAL (EO (ethylene oxide) adduct diacrylate (structure shown below) of bisphenol A, manufactured by Kyoeisha Chemical Co., Ltd., viscosity: 1,000 to 1,300 mPa ⁇ S (25 °C)
  • Polyfunctional (meth) acryloyloxy group-containing compound 7 TMPTA (trimethylolpropane triacrylate (the following structure), manufactured by Daicel-Ornesque, average molecular weight Mw: 286, viscosity: 100 mPa ⁇ s (25 ° C.))
  • Nonionic Oligomer 1 Footage 602A (a specific nonionic oligomer having a (meth) acryloyloxy group, manufactured by Neos)
  • Specific nonionic oligomer 2 Footage 681 (specific nonionic oligomer having a (meth) acryloyloxy group, manufactured by Neos)
  • Specific Nonionic Oligomer 3 Footage 710FL (a specific nonionic oligomer having no (meth) acryloyloxy group, manufactured by Neos)
  • Photopolymerization initiator 1 Irgacure 2959 ( ⁇ -hydroxyacetophenone photopolymerization initiator, 1- [4
  • the cured films obtained from the compositions of Examples 1 to 11 in which the specific nonionic oligomer and dry silica were used in combination exhibited excellent recoatability.
  • the cured films obtained from the compositions of Examples 1 to 6 and 8 to 10 containing Compound A described above as the polyfunctional (meth) acryloyloxy group-containing compound showed more excellent recoating properties.
  • the cured films obtained from the compositions of Examples 1, 2, 4 to 6 and 8 to 10 in which the specific nonionic oligomer has a (meth) acryloyloxy group showed excellent transparency.
  • the cured films obtained from the compositions of Comparative Examples 1 to 3 that did not contain the specific nonionic oligomer and the composition of Comparative Example 4 that did not contain the dry silica had insufficient recoatability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
PCT/JP2017/016498 2016-05-10 2017-04-26 紫外線硬化型樹脂組成物、硬化皮膜、及び、積層体 WO2017195598A1 (ja)

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