WO2016171024A1 - Composition de résine de formation de couche pour revêtement dur et produit durci de celle-ci - Google Patents

Composition de résine de formation de couche pour revêtement dur et produit durci de celle-ci Download PDF

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Publication number
WO2016171024A1
WO2016171024A1 PCT/JP2016/061718 JP2016061718W WO2016171024A1 WO 2016171024 A1 WO2016171024 A1 WO 2016171024A1 JP 2016061718 W JP2016061718 W JP 2016061718W WO 2016171024 A1 WO2016171024 A1 WO 2016171024A1
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Prior art keywords
meth
group
resin composition
hard coat
coat layer
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PCT/JP2016/061718
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English (en)
Japanese (ja)
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江川智哉
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株式会社ダイセル
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Priority to JP2017514075A priority Critical patent/JP6147947B2/ja
Priority to CN201680011522.9A priority patent/CN107406690B/zh
Publication of WO2016171024A1 publication Critical patent/WO2016171024A1/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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a resin composition for forming a hard coat layer and a cured product thereof.
  • the present invention also relates to a coated product obtained using the above resin composition for forming a hard coat layer.
  • Liquid crystal monitors such as liquid crystal displays, organic EL displays, and plasma displays have a protective film attached to them, which prevents the screen from being damaged, makes it difficult for fingerprints to adhere to the screen, and stains attached to the screen. The effect of making it easy to wipe off is obtained.
  • a hard coat layer for imparting scratch resistance is formed on the surface of the protective film. In recent years, there are many demands for increasing the surface hardness of the liquid crystal protective film, and there is a demand for improving the performance of the hard coat layer.
  • the polyfunctionalization of the curable group of the curable compound forming the hard coat layer is widely used as a means for improving the surface hardness of the hard coat layer.
  • a polyfunctionalized curable compound causes an increase in resin density, that is, curing shrinkage before and after curing. And the more functionalized, the more remarkable the shrinkage of curing, and the problem is that the protective film exhibits curling properties.
  • Patent Document 3 a method using a surface-modified inorganic filler in which the outer shell of inorganic particles is surface-modified with an organic substance.
  • Patent Document 3 a method using a surface-modified inorganic filler in which the outer shell of inorganic particles is surface-modified with an organic substance.
  • an object of the present invention is to provide a resin composition for forming a hard coat layer that gives a cured product having higher surface hardness and scratch resistance while suppressing the development of curling properties.
  • “Curlability” means a property that causes curling of a base material when a cured film (cured coating film) is formed on the base material. This means that the material is less likely to curl.
  • the present inventor has found that the polyfunctional alicyclic epoxy compound, the polyfunctional (meth) acrylic compound, and the epoxy group and / or polyfunctional (meth) of the polyfunctional alicyclic epoxy compound.
  • a resin composition containing a specific proportion of inorganic particles having a functional group reactive to the (meth) acryloyl group of an acrylic compound suppresses the expression of curling properties when irradiated with active energy rays, that is, has a low curl. It has been found that a cured product having higher surface hardness and scratch resistance can be obtained with high properties (or low cure shrinkage). The present invention has been completed based on these findings.
  • the present invention relates to a polyfunctional alicyclic epoxy compound (A) having an alicyclic structure and two or more epoxy groups in one molecule (polyfunctional having two or more (meth) acryloyl groups in one molecule ( Surface having a reactive functional group with an epoxy group and / or a (meth) acryloyl group on the surface of an inorganic particle having a meth) acrylic compound (B) and an average particle diameter (by dynamic light scattering method) of 0.1 to 100 nm It contains modified inorganic particles (C), a photocationic polymerization initiator (D), and a photoradical polymerization initiator (E), and the content of (A) is the sum of the content of (A) and (B).
  • a resin composition for forming a hard coat layer that is 3 to 35% by weight of (100% by weight).
  • the present invention also provides the resin composition for forming a hard coat layer, wherein the content of (C) is 5 to 40 parts by weight with respect to 100 parts by weight of the total content of (A) and (B). I will provide a.
  • the concentration of the (meth) acryloyl group in the total amount of (A), (B), (C) contained in the resin composition for forming a hard coat layer is more than 5.0 mmol / g.
  • a hard coat layer forming resin composition is provided.
  • the present invention also provides the resin composition for forming a hard coat layer, wherein the inorganic particles in the surface-modified inorganic particles (C) are silica.
  • the present invention further includes a silicon compound, a perfluoroalkyl group-containing (meth) acrylic compound, a silyl group-containing (meth) acrylic compound having a reactive functional group with an epoxy group and / or a (meth) acryloyl group, Polyether-modified (meth) acrylic compound, silicon-modified poly (meth) acrylate, polyether-modified poly (meth) acrylate, perfluoroalkyl group-containing poly (meth) acrylate, perfluoroalkyl group-containing polyether-modified (meth) acrylate, Contains at least one compound selected from acrylic-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, perfluoroalkyl group-containing polydimethylsiloxane, and polyether-modified perfluoroalkyl group-containing polydimethylsiloxane That provide the hard coat layer-forming resin composition.
  • the present invention also provides a cured product of the resin composition for forming a hard coat layer.
  • the present invention also provides a coated article provided with a hard coat layer made of a cured product of the above-described resin composition for forming a hard coat layer on the surface of an article.
  • a polyfunctional alicyclic epoxy compound having an alicyclic structure and two or more epoxy groups in one molecule A
  • Compound (B) surface-modified inorganic particles having a reactive functional group with an epoxy group and / or a (meth) acryloyl group on the surface of an inorganic particle having an average particle diameter (by dynamic light scattering method) of 0.1 to 100 nm (C)
  • a photocationic polymerization initiator (D), and a photoradical polymerization initiator (E) wherein the content of (A) is the sum of the contents of (A) and (B) (100 wt.
  • (A) is a compound represented by formula (I) (an alicyclic epoxy compound).
  • (A) is (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis (3, 4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, and
  • the resin composition for forming a hard coat layer according to [1] which is at least one compound selected from the group consisting of compounds represented by formulas (I-1) to (I-10).
  • (A) is 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate and / or (3,4,3 ′, 4′-diepoxy) bicyclohexyl
  • the resin composition for hard coat layer formation as described.
  • [5] [1] to [4] wherein (B) is a compound having 3 or more (for example, 3 to 12, preferably 5 or more, particularly preferably 5 to 10) (meth) acryloyl groups.
  • the resin composition for hard-coat layer formation as described in any one of these.
  • the reactive functional group with the epoxy group and / or the (meth) acryloyl group in (C) is a group selected from a hydroxyl group, a glycidyl ether group, and an alicyclic epoxy group (preferably a cyclohexene oxide group).
  • the content of (B) is 40 to 95% by weight of the total amount of nonvolatile components contained in the resin composition Composition.
  • the concentration of the (meth) acryloyl group in the total amount of (A), (B), (C) contained in the resin composition for forming a hard coat layer is more than 5.0 mmol / g, [1] The resin composition for forming a hard coat layer according to any one of [16] to [16]. [18] The resin for forming a hard coat layer according to any one of [1] to [17], wherein the content of (C) is 1 to 30% by weight of the total amount of nonvolatile components contained in the resin composition Composition. [19] In any one of [1] to [18], the content of (C) is 5 to 40 parts by weight with respect to 100 parts by weight of the total content of (A) and (B).
  • the resin composition for hard coat layer formation as described. [20] The sum of the contents of (A) and (C) is 5 to 60% by weight of the total (100% by weight) of (A), (B) and (C), [1] to [19 ] The resin composition for hard-coat layer formation as described in any one of these. [21] The content of (D) is 1 to 10 parts by weight with respect to 100 parts by weight of the cationic curable compound (particularly the polyfunctional alicyclic epoxy compound (A)) contained in the resin composition. ] The resin composition for forming a hard coat layer according to any one of [20] to [20].
  • the content of (E) is 1 to 10 parts by weight with respect to 100 parts by weight of the radical curable compound (particularly the polyfunctional (meth) acrylic compound (B)) contained in the resin composition.
  • At least one compound selected from polyether-modified polydimethylsiloxane, perfluoroalkyl group-containing polydimethylsiloxane, and polyether-modified perfluoroalkyl group-containing polydimethylsiloxane is
  • the resin composition for hard-coat layer formation as described in any one of these.
  • the resin composition for forming a hard coat layer of the present invention has the above-described configuration, it has high surface hardness, excellent scratch resistance, and low curling property (or low curing shrinkage) when irradiated with active energy rays.
  • the resin composition for forming a hard coat layer of the present invention can be preferably used as a resin composition for forming a hard coat layer of a glass substrate. In addition to the wrinkle effect that imparts scratch resistance, the effect of preventing the glass substrate from cracking can also be exhibited.
  • the resin composition for forming a hard coat layer of the present invention contains a polyfunctional alicyclic epoxy compound (A) and a polyfunctional (meth) acrylic compound (B).
  • A polyfunctional alicyclic epoxy compound
  • B polyfunctional acrylic compound
  • (meth) acryl means acryl and / or methacryl (any one or both of acryl and methacryl), and the same applies to (meth) acrylate and the like.
  • the polyfunctional alicyclic epoxy compound (A) is a cationic curable compound having an alicyclic structure and two or more epoxy groups in one molecule.
  • a polyfunctional alicyclic epoxy compound (A) can be used individually by 1 type or in combination of 2 or more types.
  • polyfunctional alicyclic epoxy compound (A) Compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (ii) Compound having an epoxy group directly bonded to the alicyclic ring by a single bond (Iii) Examples include compounds having an alicyclic ring and a glycidyl group.
  • Examples of the compound (i) having an alicyclic epoxy group include compounds represented by the following formula (I) (alicyclic epoxy compounds).
  • X represents a single bond or a linking group (a divalent group having one or more atoms).
  • the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. And a group in which a plurality of are connected.
  • a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (I).
  • Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like.
  • Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
  • divalent alicyclic hydrocarbon group examples include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.
  • alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized include, for example, vinylene group, propenylene group, 1-butenylene group And straight or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, and the like.
  • the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.
  • the linking group in X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxy.
  • Representative examples of the compound represented by the above formula (I) include (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2- Epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane, 1,2-bis (3,4- And epoxycyclohexane-1-yl) ethane and compounds represented by the following formulas (I-1) to (I-10).
  • L in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, and in particular, a linear or branched chain having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group. -Like alkylene groups are preferred.
  • N 1 to n 8 in the following formulas (I-5), (I-7), (I-9) and (I-10) each represents an integer of 1 to 30.
  • Examples of the compound (ii) having an epoxy group directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (II).
  • R ′ is a group obtained by removing p hydroxyl groups (—OH) from the structural formula of p-valent alcohol (p-valent organic group), and p and n each represent a natural number.
  • the p-valent alcohol [R ′-(OH) p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol.
  • p is preferably 1 to 6, and n is preferably 1 to 30.
  • n in each square bracket (outer bracket) group may be the same or different.
  • Examples of the compound (iii) having an alicyclic ring and a glycidyl group described above include a compound obtained by hydrogenating a bisphenol A type epoxy compound (hydrogenated bisphenol A type epoxy compound), a compound obtained by hydrogenating a bisphenol F type epoxy compound ( Hydrogenated bisphenol F type epoxy compound), hydrogenated biphenol type epoxy compound, hydrogenated phenol novolak type epoxy compound, hydrogenated cresol novolak type epoxy compound, hydrogenated cresol novolak type epoxy compound of bisphenol A, hydrogenated naphthalene type epoxy compound, Examples thereof include hydrogenated aromatic glycidyl ether-based epoxy compounds such as hydrogenated epoxy compounds of epoxy compounds obtained from trisphenolmethane.
  • the polyfunctional alicyclic epoxy compound (A) is preferably a compound having (i) an alicyclic epoxy group in that a cured product having low curling property, high surface hardness and excellent transparency can be obtained.
  • 4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate [compound represented by the above formula (I-1), trade name “Celoxide 2021P” (manufactured by Daicel Corporation), etc.], and (3, 4,3 ′, 4′-diepoxy) bicyclohexyl is particularly preferred.
  • the content (blending amount) of (A) is, for example, 3 to 50% by weight of the total amount of nonvolatile components (components other than the solvent) contained in the resin composition of the present invention, and the upper limit is preferably 38% by weight, Particularly preferred is 33% by weight, most preferred 29% by weight, particularly preferred 25% by weight.
  • the lower limit is preferably 6% by weight, particularly preferably 10% by weight, most preferably 13% by weight, particularly preferably 17% by weight.
  • the content (blending amount) of (A) is 3 to 35% by weight, preferably 10 to 33% by weight, particularly preferably 13% of the sum (100% by weight) of the contents of (A) and (B). ⁇ 29% by weight, most preferably 17-25% by weight.
  • the effect of reducing curling properties can be obtained while maintaining scratch resistance.
  • the content of (A) exceeds the above range, the content of the polyfunctional (meth) acrylic compound (B) described later is reduced, so that reverse curling properties are exhibited, and it is difficult to obtain a cured product with low curling properties. Become. Moreover, there exists a tendency for abrasion resistance to fall.
  • the content of (A) is less than the above range, the content of the polyfunctional (meth) acrylic compound (B) described later becomes excessive, so that positive curling properties are exhibited and a low curled cured product is obtained. It becomes difficult.
  • the polyfunctional (meth) acrylic compound (B) in the present invention is a radically curable compound having two or more (meth) acryloyl groups in one molecule.
  • a polyfunctional (meth) acryl compound (B) can be used individually by 1 type or in combination of 2 or more types.
  • the number (total number) of acryloyl groups and / or methacryloyl groups in the molecule of the polyfunctional (meth) acrylic compound (B) is 2 or more, for example 2 to 15, more preferably 3 or more (for example 3 To 12), more preferably 5 or more (for example, 5 to 10).
  • the molecular weight of the polyfunctional (meth) acrylic compound (B) is, for example, 300 to 13000, preferably 400 to 13000, particularly preferably 500 to 10,000, and most preferably 500 to 3000.
  • the weight average molecular weight (Mw) of the polyfunctional (meth) acrylic compound (B) is, for example, 400 to 13000, preferably 500 to 10,000, and particularly preferably 500 to 3000.
  • a weight average molecular weight is a molecular weight of standard polystyrene conversion measured by GPC method.
  • polyfunctional (meth) acrylic compound (B) examples include non-aromatic (eg, aliphatic (meth) acrylate (linear or branched aliphatic (meth) acrylate), alicyclic (meth) acrylate, etc. (Meth) acrylate); aromatic (meth) acrylate and the like.
  • non-aromatic (meth) acrylate is preferable from the viewpoint of non-coloring property of the cured product, and aliphatic (meth) acrylate is particularly preferable.
  • examples of the polyfunctional (meth) acrylic compound (B) include 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and glycerin diester.
  • (Meth) acrylate ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) ) Acrylate, 1,10-decandiol di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloyl) Oxydiethoxy) phenyl] propane, and bifunctional
  • polyfunctional (meth) acrylic compound (B) for example, a commercial product such as a trade name “DPHA” (manufactured by Daicel Ornex Co., Ltd.) can be suitably used.
  • (Meth) acryloyl group (for example, (meth) acryloyl group contained in polyfunctional (meth) acrylic compound (B) in the total amount of (A), (B), (C) contained in the resin composition of the present invention ) Is, for example, more than 5.0 mmol / g (for example, more than 5.0 mmol / g and not more than 10.0 mmol / g), preferably 5.5 mmol / g or more, more preferably 6.0. It is at least mmol / g, particularly preferably at least 6.5 mmol / g, most preferably at least 7.0 mmol / g.
  • the upper limit of the (meth) acryloyl group concentration is preferably 9.5 mmol / g, more preferably 9.0 mmol / g, still more preferably 8.5 mmol / g, and particularly preferably 8.0 mmol / g. Most preferably, it is 7.5 mmol / g.
  • the content of (B) is, for example, 40 to 95% by weight of the total amount of nonvolatile components (components other than the solvent) contained in the resin composition of the present invention, and the upper limit is preferably 90% by weight, more preferably 85%. % By weight, particularly preferably 80% by weight, most preferably 75% by weight.
  • the lower limit is preferably 45% by weight, more preferably 50% by weight, and particularly preferably 55% by weight.
  • the content (blending amount) of (B) is 65 to 97% by weight, preferably 65 to 94% by weight of the sum (100% by weight) of the contents of (A) and (B), more preferably Is 65 to 90% by weight, particularly preferably 65 to 87% by weight, most preferably 68 to 83% by weight, particularly preferably 73 to 83% by weight.
  • the effect of reducing the curling property can be obtained while maintaining the scratch resistance.
  • the content of (B) exceeds the above range, the content of the above-mentioned polyfunctional alicyclic epoxy compound (A) decreases, so that positive curling properties are expressed and it is difficult to obtain a cured product with low curling properties. Become.
  • the content of (B) is less than the above range, the content of the polyfunctional alicyclic epoxy compound (A) described above becomes excessive, so that reverse curling properties are exhibited, and a low curled cured product is obtained. It becomes difficult. Moreover, there exists a tendency for abrasion resistance to fall.
  • the surface-modified inorganic particles (C) in the present invention are reactive functional groups (that is, functional groups having reactivity with epoxy groups) with the epoxy groups and / or (meth) acryloyl groups of the polyfunctional alicyclic epoxy compound (A). , (Meth) acryloyl group-reactive functional group, or epoxy group and (meth) acryloyl group-reactive functional group) on the surface. Since the surface-modified inorganic particles (C) in the present invention have the reactive functional group, they are excellent in compatibility with organic substances. Moreover, it is excellent in dispersibility and can prevent that inorganic particles aggregate.
  • the surface modification inorganic particle (C) in this invention has a reactive functional group with an epoxy group, it couple
  • it has a reactive functional group with a (meth) acryloyl group, it binds to the polyfunctional (meth) acrylic compound (B), and the surface-modified inorganic particles (C) in the present invention have an epoxy group, a (meth) acryloyl group,
  • it has binds to the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B).
  • Excellent scratch resistance can be imparted.
  • it can prevent that haze increases or brittleness generate
  • a surface modification inorganic particle (C) can be used individually by 1 type or in combination of 2 or more types.
  • the inorganic particles include transparent inorganic particles such as silica, titania, alumina, zirconia and the like.
  • the coloration of the cured product can be suppressed, and the curing of the curable compound (that is, the polyfunctional alicyclic epoxy compound (A) or the polyfunctional (meth) acrylic compound (B)).
  • Silica is preferable in that it does not inhibit the above-mentioned and does not decompose the curable compound and its polymer.
  • the average particle diameter of the inorganic particles is 0.1 to 100 nm, preferably 1 to 50 nm, particularly preferably 3 to 20 nm.
  • the average particle diameter exceeds the above range, the transparency tends to decrease.
  • scratch resistance tends to be difficult to obtain.
  • Examples of the reactive functional group with the epoxy group and / or (meth) acryloyl group include (meth) acryloyl group, glycidyl ether group, alicyclic epoxy group, oxetanyl group, vinyl ether group, thiirane group, vinyl group, hydroxyl group. Etc.
  • a group excellent in reactivity with an epoxy group is preferable in that the scratch resistance of the polyfunctional alicyclic epoxy compound (A) can be improved, and in particular, a hydroxyl group, a glycidyl ether group, an alicyclic epoxy group ( For example, a cyclohexene oxide group) is preferable.
  • a commercial product such as a trade name “Y10C-MFK” (manufactured by Admatechs Co., Ltd.) can be suitably used.
  • the content (blending amount) of (C) is, for example, 1 to 30% by weight, preferably 3 to 25% by weight, particularly preferably the total amount of nonvolatile components (components other than the solvent) contained in the resin composition of the present invention. 4 to 20% by weight, most preferably 5 to 15% by weight.
  • the content (blending amount) of (C) is, for example, 5 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 7 parts per 100 parts by weight of the total content of (A) and (B). -25 parts by weight, particularly preferably 10-20 parts by weight, most preferably 10-15 parts by weight.
  • the sum of the contents of (A) and (C) is, for example, 5 to 60% by weight of the total (100% by weight) of the above (A), (B) and (C), and the upper limit is preferably 55%.
  • % By weight particularly preferably 50% by weight, most preferably 40% by weight.
  • the lower limit is preferably 10% by weight, particularly preferably 15% by weight, most preferably 20% by weight, particularly preferably 25% by weight.
  • the resin composition of the present invention contains inorganic particles having a reactive functional group on the surface with the epoxy group of the polyfunctional alicyclic epoxy compound (A) as the surface-modified inorganic particles (C)
  • the resin composition is In preparation, the polyfunctional alicyclic epoxy compound (A) and the surface-modified inorganic particles (C) may be added and mixed, respectively, but the composition thus obtained is When the content of the surface-modified inorganic particles (C) is large, haze tends to occur.
  • the surface-modified inorganic particles (C) are added to the resin composition, they are added in a state of being dispersed in a solvent.
  • the amount of the solvent is increased accordingly. Therefore, when the solvent content is set low, the amount of the surface-modified inorganic particles (C) that can be added is considerably limited. For this reason, the epoxy group of the polyfunctional alicyclic epoxy compound (A) is reacted with a reactive functional group (for example, a hydroxyl group) with the epoxy group of the surface-modified inorganic particle (C), or the surface-modified inorganic particle (C).
  • a reactive functional group for example, a hydroxyl group
  • the surface-modified inorganic particles (C) dispersed in the solvent are mixed with the polyfunctional alicyclic epoxy compound (A), and then the solvent is added. It is preferable to use the removed one.
  • a brand name "NANOPOX C620" made by EVONIC) etc. can be used conveniently, for example.
  • the surface-modified inorganic particles (C) having a functional group reactive with an epoxy group are dispersed in the polyfunctional alicyclic epoxy compound (A) without a solvent.
  • “Y10C-JFS” (Manufactured by Admatechs Co., Ltd.) can be preferably used.
  • the cationic photopolymerization initiator is a compound that generates an acid upon irradiation with light and initiates the curing reaction of the cationic curable compound contained in the resin composition, and serves as a cation moiety that absorbs light and a source of acid generation. It consists of an anion part.
  • Examples of the cationic photopolymerization initiator include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salt compounds, and the like. Can be mentioned.
  • a sulfonium salt compound in that a cured product having excellent curability can be formed.
  • the cation moiety of the sulfonium salt compound include (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and 4- (4-biphenylylthio) phenyl.
  • arylsulfonium ions such as -4-biphenylylphenylsulfonium ion and tri-p-tolylsulfonium ion (particularly, triarylsulfonium ion).
  • Y represents a phenyl group or a biphenylyl group.
  • Phf represents at least one hydrogen atom
  • BF 4 ⁇ [(Rf) t PF 6-t] -
  • Rf is .t represents an alkyl group in which at least 80% of the hydrogen atoms are substituted with fluorine atoms is an integer of 0 ⁇ 5
  • AsF 6 - , SbF 6 -, SbF 5 OH- and the like can be mentioned.
  • photocationic polymerization initiator in the present invention examples include (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (penta Fluorophenyl) borate, 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate, Diphenyl [4- (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, diphenyl [4-(
  • the content of the photocationic polymerization initiator (D) in the resin composition of the present invention is based on 100 parts by weight of the cationic curable compound (particularly the polyfunctional alicyclic epoxy compound (A)) contained in the resin composition. For example, 1 to 10 parts by weight, preferably 1 to 5 parts by weight, particularly preferably 2 to 4 parts by weight.
  • content of a photocationic polymerization initiator (D) is less than the said range, there exists a possibility of causing a curing defect.
  • the content of the cationic photopolymerization initiator (D) exceeds the above range, the cured product tends to be colored.
  • the radical photopolymerization initiator is a compound that generates radicals by irradiation of light and initiates a curing reaction of a radical curable compound contained in the resin composition.
  • a radical curable compound contained in the resin composition For example, benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd., Product name “Kayacure EPA”, etc., 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., product name “K
  • the content of the photo radical polymerization initiator (E) in the resin composition of the present invention is based on 100 parts by weight of the radical curable compound (particularly, the polyfunctional (meth) acryl compound (B)) contained in the resin composition. For example, 1 to 10 parts by weight, preferably 1 to 5 parts by weight, particularly preferably 1.5 to 3.5 parts by weight. If the content of the photo radical polymerization initiator (E) is below the above range, there is a risk of causing poor curing. On the other hand, when the content of the radical photopolymerization initiator (E) exceeds the above range, the cured product tends to be colored.
  • the resin composition of the present invention contains a curable compound other than the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B) (sometimes referred to as “other curable compound”). May be.
  • curable compounds include, for example, aromatic glycidyl ether type epoxy compounds, aliphatic polyhydric alcohol polyglycidyl ethers, oxetane compounds (compounds having one or more oxetanyl groups), vinyl ether compounds (having one or more vinyl ether groups). Compound) and the like.
  • the ratio of the total content of the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B) in the total amount (100% by weight) of the curable compound contained in the resin composition of the present invention is, for example, 50 % By weight or more, preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.
  • the upper limit of the total content of the polyfunctional alicyclic epoxy compound (A) and the polyfunctional (meth) acrylic compound (B) is 100% by weight.
  • the resin composition of the present invention may contain various additives within a range that does not impair the effects of the present invention.
  • Examples of the compound that imparts slipperiness include, for example, silane compounds, perfluoroalkyl group-containing (meth) acrylic compounds, silyl group-containing (meth) acrylic compounds, polyether-modified (meth) acrylic compounds, and silicon-modified poly (meth).
  • the compound preferably has a reactive functional group with an epoxy group and / or a (meth) acryloyl group (an example similar to the example in the surface-modified inorganic particles (C) can be given).
  • silane compound examples include triethylsilane and t-butyldimethylsilane.
  • perfluoroalkyl group-containing (meth) acrylic compound examples include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (Perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate and the like.
  • silyl group-containing (meth) acrylic compound examples include trimethylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tri (n-butyl) silyl (meth) acrylate, triisobutylsilyl (meth) acrylate, and tricyclohexyl.
  • examples thereof include silyl (meth) acrylate and triphenylsilyl (meth) acrylate.
  • the silicon-modified poly (meth) acrylate is a compound in which a silicon chain (for example, a polydimethylsiloxane chain) is bonded to the terminal and / or side chain of poly (meth) acrylate as a main chain.
  • a silicon chain for example, a polydimethylsiloxane chain
  • the polyether-modified poly (meth) acrylate is a compound in which a polyether chain is bonded to the terminal and / or side chain of poly (meth) acrylate as a main chain.
  • the perfluoroalkyl group-containing poly (meth) acrylate is a compound having a perfluoroalkyl group at the terminal and / or side chain of the poly (meth) acrylate as the main chain.
  • the perfluoroalkyl group-containing polyether-modified (meth) acrylate is a compound having a perfluoroalkyl group and a polyether chain at the terminal and / or side chain of the poly (meth) acrylate as the main chain.
  • the acrylic-modified polydimethylsiloxane is a compound in which a poly (meth) acrylic chain is bonded to the terminal and / or side chain of the main chain polydimethylsiloxane.
  • polyether-modified polydimethylsiloxane, the perfluoroalkyl group-containing polydimethylsiloxane, and the polyether-modified perfluoroalkyl group-containing polydimethylsiloxane are the same as described above except that the poly (meth) acrylate is changed to polydimethylsiloxane. .
  • perfluoroalkyl group examples include a perfluoroalkyl group having 3 to 30 carbon atoms such as a perfluorooctyl group.
  • a compound containing a hydroxyl group that is particularly excellent in reactivity with the epoxy group of the polyfunctional alicyclic epoxy compound (A) (for example, a hydroxyl group-containing silicon-modified poly (meth) acrylate) may be used.
  • the hydroxyl value is preferably 5 to 150 mgKOH / g, for example.
  • the amount of the compound that imparts slipperiness is the sum (100 parts by weight) of (A), (B), and (C) contained in the resin composition of the present invention.
  • it is, for example, 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight.
  • a solvent for example, butyl acetate, methyl ethyl ketone, etc.
  • a polyhydric alcohol for example, butyl acetate, methyl ethyl ketone, etc.
  • an organosiloxane compound for example, metal oxide particles, rubber particles, an antifoaming agent, a silane cup
  • Conventional additives such as ring agents, fillers, plasticizers, leveling agents, antistatic agents, mold release agents, surfactants, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbers, phosphors, etc. Can be used.
  • the content of these additives can be appropriately set within a range of, for example, 0 to 40% by weight, preferably 1 to 25% by weight, based on the resin composition (100% by weight) of the present invention.
  • the resin composition of the present invention can be prepared by stirring and mixing the above-described components while being heated as necessary.
  • the resin composition of the present invention can be used as a one-component composition in which components mixed in advance are used as they are.
  • components divided into two or more each component is 2
  • a mixture of the above components may be used as a multi-liquid composition (for example, a two-liquid composition) that is used by mixing at a predetermined ratio before use.
  • the stirring / mixing method is not particularly limited, and for example, known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, a self-revolving stirrer and the like can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.
  • known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, a self-revolving stirrer and the like can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.
  • composition for hard coat By curing the resin composition of the present invention, a cured product having low curl properties and excellent surface hardness and scratch resistance can be obtained. For this reason, the resin composition of the present invention can be preferably used as a composition for hard coat (hard coat agent).
  • the resin composition of the present invention is applied to the surface of an article [for example, a substrate or film made of metal or resin (for example, plastic such as TAC or PET)] as an object (object to be coated) and cured. By this, a painted product is obtained. Since the resin composition of the present invention has excellent curability (curing speed) and the cured product of the present invention has low curl properties and excellent surface hardness and scratch resistance, the coated product has high productivity and quality. Excellent for both.
  • the resin composition of the present invention can be cured in an extremely short time by applying an active energy ray such as an ultraviolet ray or an electron beam after being applied to an article.
  • an active energy ray such as an ultraviolet ray or an electron beam
  • a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like is used as a light source for ultraviolet irradiation.
  • the irradiation time varies depending on the type of the light source, the distance between the light source and the coating surface, and other conditions, but is several tens of seconds at most, and usually several seconds.
  • an irradiation source with a lamp output of about 80 to 300 W / cm is used.
  • an electron beam having an energy in the range of 50 to 1000 KeV and to give an irradiation amount of 2 to 5 Mrad.
  • curing may be promoted by heating (post-cure) as necessary.
  • the resin composition of the present invention comprises a coating agent (particularly for hard coat use), ink, adhesive, sealant, sealant, resist, composite material, transparent substrate, transparent film or sheet, and optical material (for example, optical lens).
  • a coating agent particularly for hard coat use
  • ink adhesive, sealant, sealant, resist, composite material, transparent substrate, transparent film or sheet
  • optical material for example, optical lens.
  • Etc. stereolithography material
  • electronic material eg, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, etc.
  • mechanical component material electrical component material
  • automotive component material civil engineering building material
  • molding It can be used for various applications such as materials, plastic forming materials, solvents (for example, reactive diluents, etc.).
  • Example 1 [Preparation of resin composition] Each component is mixed at the blending ratio shown in the table (unit: parts by weight), and stirred using a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinky Co., Ltd.) Thus, a resin composition was obtained.
  • a self-revolving stirrer trade name “Awatori Nerita AR-250”, manufactured by Shinky Co., Ltd.
  • the obtained resin composition was applied onto a PET base material (trade name “Lumirror T60”, manufactured by Toray Industries, Inc .; film thickness 100 ⁇ 5 ⁇ m) using a bar coater. At this time, it applied using the bar coater so that the film thickness after drying might be set to 20 micrometers. Then, after drying at 80 ° C. for 1 minute, it was cured by irradiating with ultraviolet rays under the condition of an irradiation amount of about 1000 mJ / cm 2 in a state where it was put in a sealed container purged with nitrogen.
  • the laminate (cured film) having the structure of “PET substrate / cured product (cured coating film)” thus obtained was used as a sample for pencil hardness evaluation and scratch resistance evaluation. Further, a test piece having a square of 10 cm on one side was cut from the laminate (cured film) having the configuration of “PET substrate / cured product (cured coating film)” obtained above. With respect to the above test piece, the film thickness at the measurement points indicated by the numbers 1 to 5 circled in FIG. 1 (1a) was measured. At all these measurement points, the case where the film thickness of the cured coating film obtained by subtracting the film thickness of the PET substrate (the film thickness measured in advance) from the film thickness at the measurement point is 20 ⁇ m ⁇ 2 ⁇ m, respectively. Was used as a sample for curl evaluation. In the case of failure, the bar coater was changed until the film thickness at the above measurement point passed, and the above coating, drying, and curing steps were repeated to prepare a sample for curl evaluation.
  • Examples 2 to 10, Comparative Examples 1 to 8 A resin composition and its cured product (sample) were obtained in the same manner as in Example 1 except that the amount of each component was changed as shown in the table.
  • post-cure heating at 80 ° C. for 2 hours was performed after ultraviolet irradiation.
  • the pencil hardness of the cured films (cured coating film thickness: about 20 ⁇ m) obtained in Examples and Comparative Examples was measured by the following method.
  • the pencil hardness of the cured coating film was evaluated according to JIS K5600. The evaluation was performed by external appearance observation, and the cured coating film on the PET base material was rubbed with a pencil. Specifically, the evaluation is first performed with a pencil with a certain hardness, and when the scratch is not found, the evaluation is repeated with the pencil with the hardness one higher. Re-evaluated by hardness. If scratches cannot be confirmed, use a pencil with a hardness of one level again. If reproducibility is confirmed twice or more, the hardness of the hardest pencil without scratches is the pencil hardness of the cured coating film.
  • the evaluation results were expressed in terms of pencil core hardness.
  • the evaluation conditions are as follows. Evaluation pencil: "Pencil hardness test pencil” manufactured by Mitsubishi Pencil Co., Ltd. Load: 750gf Scratching distance: 50 mm or more Scratching angle: 45 ° Measurement environment: 23 ° C, 50% RH In addition, the sample (cured film) used for a test used what was humidity-controlled for 24 hours with the constant temperature and humidity machine of 23 degreeC and 50% RH.
  • NANOPOX C620 Compound obtained by reacting hydroxyl group-containing silica (silica average particle size: 10 nm) (40 parts by weight) with Celoxide 2021P (60 parts by weight), trade name “NANOPOX C620”, manufactured by EVONIC Y10C-JFS: Celoxide A mixture of 2021P (80.5 parts by weight) and alicyclic epoxy group-containing silica (silica average particle size: 10 nm) (19.5 parts by weight), trade name “Y10C-JFS”, manufactured by Admatechs Corporation Celoxide 2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, trade name “Celoxide 2021P”, manufactured by Daicel Corporation A-9550: Dipentaerythritol polyacrylate, molecular weight: about 554, hydroxyl value: about 56 mg KOH / G, Shinnaka
  • DPHA dipentaerythritol hexaacrylate, molecular weight: 578, product Name “DPHA”, manufactured by Daicel Ornex Co., Ltd.
  • Y10C-MFK glycidyl ether group-containing silica (silica average particle size: 10 nm) in methyl ethyl ketone dispersion (silica concentration: 30% by weight), trade name “Y10C-MFK”, CPI-210S manufactured by Admatechs Co., Ltd .: diphenyl [4- (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, trade name “CPI-210S”, Irgacure 184: 1-hydroxycyclohexa manufactured by San Apro Co., Ltd.
  • BYK-SILCLEAN 3700 hydroxyl group-containing silicone-modified polyacrylates, hydroxyl value: about 30 mgKOH / g, trade name "BYK-SILCLEAN 3700", manufactured by BYK Chemie Japan Co.,
  • the resin composition for forming a hard coat layer of the present invention can form a cured product having high surface hardness, excellent scratch resistance, and low curl properties by irradiation with active energy rays. It can be suitably used for applications in which a hard coat layer is formed on the surface of a plastic film or glass substrate.

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Abstract

La présente invention concerne une composition de résine de formation de couche pour revêtement dur par laquelle on obtient un produit durci dans lequel on supprime l'enroulement des bords et qui présente une grande dureté superficielle ainsi qu'une grande résistance aux rayures. Cette composition de résine de formation de couche pour revêtement dur contient un composé époxyde alicyclique polyfonctionnel (A), un composé (méth)acrylique polyfonctionnel (B), des particules inorganiques à surface modifiée (C), un amorceur de photopolymérisation cationique (D) et un amorceur de photopolymérisation radicalaire (E), la teneur en composant (A) étant de 3 à 35 % en poids par rapport à la teneur totale (100 % en poids) en composants (A) et (B).
PCT/JP2016/061718 2015-04-21 2016-04-11 Composition de résine de formation de couche pour revêtement dur et produit durci de celle-ci WO2016171024A1 (fr)

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WO2017183226A1 (fr) * 2016-04-18 2017-10-26 Jnc株式会社 Composition de résine thermodurcissable, film durci, substrat pourvu du film durci et composant électronique
WO2019026460A1 (fr) * 2017-08-04 2019-02-07 株式会社ダイセル Composition de résine pour la formation d'une couche de revêtement dur
CN111065669A (zh) * 2017-09-15 2020-04-24 住友化学株式会社 固化性组合物
US11827796B2 (en) 2018-04-16 2023-11-28 Canon Kabushiki Kaisha Curable resin composition for three-dimensional shaping and method of manufacturing three-dimensionally shaped product

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US11914186B2 (en) 2018-04-16 2024-02-27 Sumitomo Electric Industries, Ltd. Optical fiber
ES2962722T3 (es) * 2018-08-08 2024-03-20 Mitsubishi Gas Chemical Co Composición de recubrimiento duro, película laminada y película curable
CN112601724B (zh) * 2018-08-22 2022-09-20 住友电气工业株式会社 光纤
CN116948523B (zh) * 2023-02-03 2024-05-03 北京驳凡科技有限公司 一种uv树脂组合物及其应用

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WO2017183226A1 (fr) * 2016-04-18 2017-10-26 Jnc株式会社 Composition de résine thermodurcissable, film durci, substrat pourvu du film durci et composant électronique
WO2019026460A1 (fr) * 2017-08-04 2019-02-07 株式会社ダイセル Composition de résine pour la formation d'une couche de revêtement dur
JPWO2019026460A1 (ja) * 2017-08-04 2020-08-06 株式会社ダイセル ハードコート層形成用樹脂組成物
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CN111065669B (zh) * 2017-09-15 2022-07-15 住友化学株式会社 固化性组合物
US11827796B2 (en) 2018-04-16 2023-11-28 Canon Kabushiki Kaisha Curable resin composition for three-dimensional shaping and method of manufacturing three-dimensionally shaped product

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