WO2015145798A1 - Article moulé en résine et corps stratifié l'utilisant - Google Patents

Article moulé en résine et corps stratifié l'utilisant Download PDF

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Publication number
WO2015145798A1
WO2015145798A1 PCT/JP2014/070863 JP2014070863W WO2015145798A1 WO 2015145798 A1 WO2015145798 A1 WO 2015145798A1 JP 2014070863 W JP2014070863 W JP 2014070863W WO 2015145798 A1 WO2015145798 A1 WO 2015145798A1
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Prior art keywords
resin molded
meth
acrylate
same
component
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PCT/JP2014/070863
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English (en)
Japanese (ja)
Inventor
隆太 斎藤
康弘 上之
芳昭 宮本
敏哉 上野
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グンゼ株式会社
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Publication of WO2015145798A1 publication Critical patent/WO2015145798A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a resin molded body and a laminate using the same.
  • a film-like resin molded body has been used for a substrate of a display such as a liquid crystal display or an organic electroluminescence (EL) display.
  • a display such as a liquid crystal display or an organic electroluminescence (EL) display.
  • the above-mentioned display is widely used as a touch panel for combining an input means (pointing device) with an electronic device such as a personal digital assistant (PDA), a notebook PC, an OA device, a medical device, or a car navigation system. It is used.
  • PDA personal digital assistant
  • a resistance type, an electromagnetic induction type, an optical type, and a capacitance type also referred to as a capacitive coupling type are known.
  • a transparent film when disposed as the transparent planar member, it has a surface hardness to withstand the pressure of the fingertip accompanying input from the user and protect the liquid crystal layer of the LCD, Moreover, it is required to be lightweight.
  • a resin molded body containing a specific polyfunctional urethane (meth) acrylate, a specific bifunctional (meth) acrylate, and a photopolymerization initiator as a film-shaped resin molded body having a surface hardness used for such a display Has been proposed (see, for example, Patent Document 1).
  • Patent Document 1 since pressure is frequently applied to the touch panel during input, a particularly high surface hardness is required, and the resin molded body disclosed in Patent Document 1 cannot be said to have sufficient surface hardness.
  • the resin molded body is required to have high surface hardness and appropriate flexibility.
  • An object of the present invention is to provide a resin molded body having a very high surface hardness and moderate flexibility, and having sufficient hardness and flexibility, and a laminate using the resin molded body.
  • the present inventor has cured a polymerizable composition containing a specific polyfunctional urethane (meth) acrylate and a specific bifunctional (meth) acrylate.
  • the present inventors have found that the object can be achieved by forming a molded body, and have completed the present invention.
  • this invention relates to the following resin molding and a laminated body using the same.
  • Resin molded body obtained by curing a polymerizable composition containing the following components (A) and (B): (A) a polyfunctional urethane (meth) acrylate obtained by reacting a polyisocyanate compound (excluding those having an alicyclic structure) and a hydroxyl group-containing (meth) acrylate, (B) A bifunctional (meth) acrylate having an alicyclic structure.
  • Item 2 The resin molded article according to Item 1, wherein the component (A) is a polyfunctional urethane (meth) acrylate represented by the following general formula (1).
  • R ⁇ 1 >, R ⁇ 2 > and R ⁇ 3 > are the same or different, and show the functional group which does not have an alicyclic structure which has a (meth) acryloyl group and a urethane bond.
  • Item 3 The resin molded article according to Item 1 or 2, wherein the component (A) is a polyfunctional urethane (meth) acrylate represented by the following general formula (2).
  • R 4 , R 5 and R 6 are the same or different and each represents an alkyl group having 1 to 10 carbon atoms; R 7 to R 15 are the same or different and each represents a hydrogen atom or a methyl group; n, m and k are the same or different and represent an integer of 1 to 3.) 4).
  • the mass ratio (M A ) / (M B ) between the mass (M A ) of the component ( A ) and the mass (M B ) of the component (B) in the polymerizable composition is 30/70 to 70/30.
  • Item 6. The resin molded article according to any one of Items 1 to 5. 7).
  • the component (B) is at least one selected from the group consisting of bifunctional (meth) acrylates represented by the following general formulas (3) to (5), Resin molded body.
  • R 16 and R 17 are the same or different and each represents an alkylene group which may contain an ether bond having 1 to 6 carbon atoms; R 18 and R 19 are the same or different and represent a hydrogen atom or Represents a methyl group, a represents 1 or 2, and b represents 0 or 1.
  • R 20 and R 21 are the same or different and each represents an alkylene group which may contain an ether bond having 1 to 6 carbon atoms; R 22 and R 23 are the same or different and represent a hydrogen atom or Indicates a methyl group.
  • R 24 and R 25 are the same or different and each represents a hydrogen atom or a methyl group, and R 26 and R 27 may be the same or different and may contain an ether bond having 1 to 6 carbon atoms.
  • An alkylene group, and R 28 and R 29 are the same or different and represent a hydrogen atom or a methyl group.
  • Item 8 The resin molded article according to any one of Items 1 to 7, wherein the polymerizable composition further contains a component (C) a photopolymerization initiator. 9.
  • Component (C) is a benzoin derivative, benzyl ketal, ⁇ -hydroxyacetophenone, ⁇ -aminoacetophenone, acylphosphine oxide, titanocene, O-acyloxime type initiator, a mixture of benzophenone and amine, Michler's ketone and benzophenone.
  • Item 9 The resin molded article according to Item 8, which is at least one selected from the group consisting of a mixture and a mixture of thioxanthone and amine. 10. 10.
  • a laminate comprising a gas barrier film formed on at least one surface of the resin molded article according to any one of items 1 to 9. 11.
  • 10. A laminate comprising a transparent conductive film formed on at least one surface of the resin molded article according to any one of items 1 to 9. 12 Item 12.
  • the resin molded body of the present invention is a polyfunctional urethane (meth) obtained by reacting (A) a polyisocyanate compound (excluding those having an alicyclic structure) and a hydroxyl group-containing (meth) acrylate. It is a resin molding formed by curing a polymerizable composition containing an acrylate and (B) a bifunctional (meth) acrylate having an alicyclic structure.
  • the resin molded body of the present invention uses a polyfunctional urethane (meth) acrylate obtained by reacting a polyisocyanate compound having no alicyclic structure and a hydroxyl group-containing (meth) acrylate, particularly as the component (A). Since it is polyfunctional, it can be cured to form a crosslinked structure, and a resin molded body having high hardness can be obtained. Moreover, since the compound which does not have an alicyclic structure is used as a polyisocyanate compound, when a film etc. are formed using a resin molding, the surface hardness of the said film is remarkably excellent.
  • the hardness is improved, but the flexibility of the resin molded body is lowered to deteriorate the flexibility, and the impact resistance is lowered to become brittle.
  • the resin molded body of the present invention since the acrylate of the component (A) has a urethane group in the molecule, the resin molded body has appropriate toughness due to hydrogen bonding and is suppressed from becoming brittle. . For this reason, the resin molded body of the present invention becomes a resin molded body excellent in flexibility, having excellent mechanical strength such as flexibility and impact resistance, while having a highly crosslinked structure.
  • bifunctional or higher functional (meth) acrylate compounds have large shrinkage during polymerization, and the cured product cracks in the mold or breaks during mold removal. Have difficulty. Since the resin molded body of the present invention has a urethane group and has hardness and appropriate flexibility, the resin molded body can be obtained with improved strength and high yield.
  • the resin molded body of the present invention since the resin molded body of the present invention has the above-described configuration, it is a resin molded body having the characteristics that the surface hardness is remarkably excellent and at the same time exhibits excellent flexibility. Resin moldings having such characteristics are particularly required in fields such as touch panels and flexible displays, and are useful for touch panel substrates and the like.
  • Component (A) is a polyfunctional urethane (meth) acrylate obtained by reacting a polyisocyanate compound (excluding those having an alicyclic structure) and a hydroxyl group-containing (meth) acrylate.
  • polyisocyanate compound which does not have an alicyclic structure in a molecule
  • numerator as said polyisocyanate compound
  • aliphatic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate are mentioned. .
  • Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate.
  • HDI hexamethylene diisocyanate
  • pentamethylene diisocyanate 1,2-propylene diisocyanate
  • 2,3-butylene diisocyanate 1,3-butylene diisocyanate
  • dodecamethylene diisocyanate dodecamethylene diisocyanate.
  • Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3 , 5-triisocyanatebenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 2 , 4-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate (MDI), and the like.
  • MDI polymethylene polyphenylene polyisocyanate
  • the aromatic aliphatic polyisocyanates include ⁇ , ⁇ ′-diisocyanate-1,3-dimethylbenzene, ⁇ , ⁇ ′-diisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ ′-diisocyanate-1,4-diethylbenzene, 1 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.
  • polyisocyanate compound it is preferable to use an aliphatic polyisocyanate from the viewpoint that yellowing of the resin molded product can be suppressed.
  • polyisocyanate compound allophanate type polyisocyanate, biuret type polyisocyanate, amide group-containing polyisocyanate, trimethylolpropane adduct obtained from the above-mentioned aliphatic polyisocyanate, aromatic polyisocyanate, or araliphatic polyisocyanate.
  • Type polyisocyanate and isocyanurate type polyisocyanate can be used.
  • the above polyisocyanate compound may be used alone or in combination of two or more.
  • the hydroxyl group-containing (meth) acrylate is not particularly limited as long as it has a hydroxyl group and a (meth) acryloyl group in the molecule.
  • the hydroxyl group-containing (meth) acrylate one having no alicyclic structure in the molecule is preferably used from the viewpoint of suppressing the surface hardness and color change of the resin molded product.
  • the above hydroxyl group-containing (meth) acrylate may be used alone or in combination of two or more.
  • a catalyst can be used for the reaction of the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate.
  • a conventionally known organotin compound can be used as the catalyst. Specifically, stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyl Tin dilaurate, dibutyltin dichloride, dioctyltin dilaurate and the like can be mentioned.
  • Component (A) is preferably a polyfunctional urethane (meth) acrylate represented by the following general formula (1).
  • R ⁇ 1 >, R ⁇ 2 > and R ⁇ 3 > are the same or different, and are a functional group which has a (meth) acryloyl group and a urethane bond, and does not have an alicyclic structure.
  • component (A) is preferably a polyfunctional urethane (meth) acrylate represented by the following general formula (2).
  • R 4 , R 5 and R 6 are the same or different and each represents an alkyl group having 1 to 10 carbon atoms.
  • R 4 , R 5 and R 6 are the same or different and are preferably alkyl groups having 1 to 6 carbon atoms. If the number of carbon atoms of R 4 , R 5 and R 6 is too large, the crosslink density may decrease and the resin molded body may not have sufficient hardness.
  • R 7 to R 15 are the same or different and each represents a hydrogen atom or a methyl group.
  • R 7 to R 15 are preferably hydrogen atoms from the viewpoint of excellent reactivity.
  • n, m and k are preferably the same or different and each represents an integer of 1 to 3.
  • the flexural modulus of the resin composition may be too large.
  • n, m and k are preferably 2.
  • the number average molecular weight of component (A) is preferably 200 to 5,000. More preferably, it is 400 to 3000, and still more preferably 500 to 2500. If the number average molecular weight is less than 200, curing shrinkage increases and birefringence tends to occur. When the number average molecular weight exceeds 5,000, the crosslinkability is lowered and the heat resistance may be insufficient.
  • the content of the component (A) in the polymerizable composition for forming the resin molded body is not particularly limited, but is preferably 10 to 50% by mass with respect to 100% by mass of the polymerizable composition. More preferably, it is ⁇ 30% by mass.
  • the content of the component (A) in the polymerizable composition for forming the resin molded body is not particularly limited, but is preferably 10 to 50% by mass with respect to 100% by mass of the polymerizable composition. More preferably, it is ⁇ 30% by mass.
  • Component (B) is a bifunctional (meth) acrylate having an alicyclic structure.
  • pentadecane acrylate methacrylate, 2,2-bis [4- ( ⁇ -methacryloyloxyethoxy) cyclohexyl] propane, 1,3-bis (methacryloyloxymethyl) cyclohexane, 1,3-bis (methacryloyloxyethyl) Bifunctional (meth) acrylates such as oxymethyl) cyclohexane, 1,4-bis (methacryloyloxymethyl) cyclohexane, 1,4-bis (methacryloyloxyethyloxymethyl) cyclohexane, 1,3,5-tris (methacryloyloxymethyl) And trifunctional (meth) acrylates such as cyclohexane and 1,3,5-tris (methacryloyloxyethyloxymethyl) cyclohexane.
  • bifunctional (meth) acrylate is used from a flexible point. From the viewpoint of heat
  • the component (B) is preferably at least one bifunctional (meth) acrylate selected from the following general formulas (3), (4) and (5) from the viewpoint of optical performance, and more preferably bifunctional methacrylate. .
  • R 16 and R 17 are the same or different and each represents an alkylene group which may contain an ether bond having 1 to 6 carbon atoms;
  • R 18 and R 19 are the same or different and represent a hydrogen atom or methyl Represents a group, a represents 1 or 2, and b represents 0 or 1.
  • R 20 and R 21 are the same or different and each represents an alkylene group which may contain an ether bond having 1 to 6 carbon atoms;
  • R 22 and R 23 are the same or different and represent a hydrogen atom or a methyl group; Indicates a group.
  • R 24 and R 25 are the same or different and each represents a hydrogen atom or a methyl group
  • R 26 and R 27 are the same or different and may contain an ether bond having 1 to 6 carbon atoms
  • R 28 and R 29 are the same or different and each represents a hydrogen atom or a methyl group.
  • the content of the component (B) in the polymerizable composition for forming the resin molded body is not particularly limited, but is preferably 10 to 40% by mass with respect to 100% by mass of the polymerizable composition. More preferably, it is ⁇ 20% by mass.
  • the content of the component (B) in the polymerizable composition for forming the resin molded body is not particularly limited, but is preferably 10 to 40% by mass with respect to 100% by mass of the polymerizable composition. More preferably, it is ⁇ 20% by mass.
  • the mass ratio (M A ) / (M B ) between the mass (M A ) of the component ( A ) and the mass (M B ) of the component (B) in the polymerizable composition ranges from 30/70 to 70. / 30 is preferable. If the mass ratio of the component (A) is less than 30, the mechanical properties such as surface hardness and impact resistance may be inferior. If the mass ratio of the component (A) exceeds 70, the water absorption rate may increase. is there. A more preferable range of the mass ratio is 40/60 to 60/40, and a further preferable range is 45/55 to 55/45.
  • the said polymeric composition may contain the component (C) which is a photoinitiator other than a component (A) and a component (B).
  • Component (C) is not particularly limited as long as it can be used as a photopolymerization initiator.
  • benzoin derivative benzyl ketal, ⁇ -hydroxyacetophenone, ⁇ -aminoacetophenone, acylphosphine oxide, titanocenes, O-acyloxy Type initiator, benzophenone / amine photopolymerization initiator (mixture of benzophenone and amine), Michler ketone / benzophenone photopolymerization initiator (mixture of Michler ketone and benzophenone), thioxanthone / amine photopolymerization initiator (thioxanthone and Specific examples include 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, and the like.
  • the content of the component (C) in the polymerizable composition is not particularly limited, but is 0.1 to 5 mass with respect to a total of 100 mass parts of the content of the component (A) and the content of the component (B). Part is preferable, 0.2 to 4 parts by mass is more preferable, and 0.3 to 3 parts by mass is still more preferable.
  • content of a component (C) exceeds 5 mass parts, there exists a possibility that the retardation of a resin molding may increase, and there exists a possibility that the light transmittance in 400 nm may fall.
  • the content of the component (C) is less than 0.1 parts by mass, the polymerization rate may decrease and the polymerization may not proceed sufficiently.
  • the other component may be included in the range which does not impair the physical property of the resin molding of this invention.
  • the other components include polyfunctional polyester acrylates having three or more functions other than components (A) and (B), monomers having ethylenically unsaturated bonds other than components (A) and (B), and an increase.
  • Examples include sensitizers, polymerization inhibitors, thermal polymerization initiators, antioxidants, ultraviolet absorbers, antifoaming agents, leveling agents, bluing agents, dyes and pigments, fillers, and the like.
  • polyester acrylate other than the components (A) and (B) examples include polyester acrylate obtained by esterifying a polyol, a polyvalent carboxylic acid, and (meth) acrylic acid.
  • polystyrene resin examples include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3-butanediol.
  • Neopentyl glycol hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, , 2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4 4′-diol, 2,6-decalin glycol, trimethylolpropane, 3-methyl-1,5-pentanediol, ethylene oxide or propylene oxide adduct, glycerin, trimethylolethane, pentaerythritol, dimethylolpropionic acid, Examples include dimethylol butanoic acid.
  • polyvalent carboxylic acid examples include hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1, Examples thereof include 12-dodecanedioic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid and the like.
  • the polyol and polyvalent carboxylic acid may be used alone or in combination of two or more.
  • Examples of monomers having an ethylenically unsaturated bond other than the above components (A) and (B) include methyl methacrylate, 2-hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl ( Monofunctional (meth) acrylates such as (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, di (meth) acrylate of polyethylene glycol higher than tetraethylene glycol, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy 1,3-di (meth) acryloxypro Bread, 2,2-bis [4- (meth) acryloyloxypheny
  • Examples of the sensitizer include thiol compounds and amine compounds.
  • thermal polymerization initiator known compounds can be used.
  • hydroperoxide such as hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide
  • dialkyl peroxides such as t-butyl peroxybenzoate, peroxyesters such as t-butylperoxy (2-ethylhexanoate)
  • diacyl peroxides such as benzoyl peroxide
  • peroxycarbonates such as diisopropyl peroxycarbonate
  • peroxides such as peroxyketal and ketone peroxide.
  • the ultraviolet absorber is not particularly limited, and a conventionally known ultraviolet absorber can be used, but an ultraviolet absorber represented by the following formula (6) is preferably used.
  • the resin molded body is excellent not only in weather resistance but also in suppressing yellowing of the film.
  • the above-mentioned polymerizable composition preferably has a viscosity at 20 ° C. of 1000 to 4000 mPa ⁇ s, more preferably 2000 to 3000 mPa ⁇ s. If the viscosity is less than 1000 mPa ⁇ s, unpolymerized monomers may easily remain in the molding process. If the viscosity exceeds 4000 mPa ⁇ s, it is difficult to inject into the mold when batch-type casting is performed. In addition, there is a risk that retardation is likely to increase due to flow unevenness. Examples of the method for adjusting the viscosity of the polymerization composition within the above range include a method for appropriately adjusting the types and blending amounts of the components (A) and (B).
  • the resin molded body of the present invention can be obtained by curing the polymerizable composition.
  • the flexibility of the resin molded body is preferably ⁇ 14 or less, and more preferably ⁇ 12 or less. If the evaluation of flexibility is too low, there is a risk of cracking or cracking when the resin molding is used in a flexible display, etc. If the evaluation of flexibility is too high, the resin molding is used for a touch panel or the like. There is a possibility that the surface hardness is not sufficient.
  • the above flexibility can be measured with a bending tester according to JIS K5600-5-1.
  • the light transmittance of the resin molding is preferably 90% or more. If the light transmittance is less than 90%, the brightness of the display device may not be secured, and if the emission intensity is increased to secure the brightness, the power consumption may be increased.
  • the light transmittance is a spectral light transmittance at a wavelength of 400 to 700 nm, and includes reflection on both sides of the resin molded body. At any wavelength in this wavelength range, the resin usually absorbs light in the vicinity of 400 nm close to the ultraviolet region, but the resin molded product of the present invention preferably has a light transmittance of 90% or more at this 400 nm.
  • a more preferable range of light transmittance is 91% or more, particularly preferably 92% or more over the entire range of 400 to 700 nm.
  • the light transmittance can be adjusted to the above-described range by, for example, a method of appropriately selecting the types and blending amounts of the components (A), (B), and (C).
  • the light transmittance can be measured using a turbidimeter (NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.) by a measuring method based on JIS K7361.
  • the refractive index of the resin molded body is preferably 1.49 to 1.53, more preferably 1.50 to 1.52. If the refractive index is too high, the light transmittance of the resin molding may be reduced. If the refractive index is too low, when a gas barrier layer, a transparent conductive layer, or the like is laminated on the resin molded body, interface reflection at the interface between these layers may increase.
  • a refractive index can be adjusted to the above-mentioned range, for example by the method of selecting suitably the kind and compounding quantity of the said component (A), (B) and (C).
  • the refractive index can be measured using a turbidimeter (NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.) by a measuring method based on JIS K7361.
  • the retardation of the resin molded body is preferably 10 or less.
  • the retardation is more preferably 5 nm or less, and further preferably 2 nm or less. If the retardation is too large, the polarized light transmitted through the resin molded body cannot maintain its polarization characteristics. Therefore, when the resin molded body is used for a liquid crystal display, the fineness of the image may be reduced. Retardation can be adjusted to the above-mentioned range by the method of selecting suitably the viscosity of polymeric composition, and the irradiation method of the active energy ray at the time of making it harden
  • the retardation can be measured with a phase difference measuring device.
  • the glass transition point of the resin molding is preferably 120 ° C. or higher.
  • the glass transition point is more preferably 160 ° C. or higher, and further preferably 200 ° C. or higher. If the glass transition point is too low, when the resin molded body is used in a display device such as a liquid crystal television, the display device may be deformed and the display device may be unreliable. Since liquid crystal televisions in recent years use a powerful backlight, the temperature of the substrate using the resin molded body may rise to nearly 120 ° C.
  • a glass transition point can be adjusted to the above-mentioned range by the method of selecting suitably the kind and compounding quantity of the said component (A) and (B), for example.
  • the glass transition point can be measured using a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation).
  • the linear expansion coefficient of the resin molded body is preferably 30 to 60 ppm / ° C, and more preferably 40 to 50 ppm / ° C. If the linear expansion coefficient is too low, the difference from other optical films becomes large, and the fineness of the image may be reduced. If the linear expansion coefficient is too high, when a device is manufactured using a resin molded body, the dimensional change of the device becomes large, and there is a possibility that the pixel and the wiring are liable to be displaced.
  • a linear expansion coefficient can be adjusted to the above-mentioned range by the method of selecting suitably the kind and compounding quantity of the said component (A) and (B), for example.
  • the linear expansion coefficient can be measured by measuring the elongation of the test piece when the temperature is raised to 25 to 100 ° C. using a thermal analyzer (TMA-50 manufactured by Shimadzu Corporation).
  • the method for producing the resin molded body of the present invention is not particularly limited as long as the polymerizable composition can be cured to obtain a molded body.
  • coating process, (3) wet laminating process, (4) hardening process, (5) base material peeling process process, and (6) winding-up process is mentioned.
  • this process order is shown as an example, and the manufacturing method is not limited to this process order. Further, the order of the steps may be adjusted as appropriate so that any one of them is performed at the same time, the number of steps is increased, or these steps are performed individually.
  • the polymer composition coating step and the layer thickness adjusting step of the polymer composition are performed in parallel, and in the above (3) The wet laminating process and the layer thickness adjusting process of the polymer composition are performed in parallel.
  • FIG. 1 is a schematic diagram showing an example of (1) polymer composition preparation step, (2) polymer composition coating step, (3) wet lamination treatment step, and (4) curing step of the above production method. is there.
  • the manufacturing method is performed by a manufacturing apparatus 100.
  • the manufacturing apparatus 100 includes a tray 102 for containing a polymer composition, a backup roller 103, a roll knife 104, and a roller 105A, which are arranged to face each other at a predetermined interval in parallel in the axial direction (along a direction perpendicular to the paper surface). , 105B, and the UV irradiation device 107.
  • the PET substrate 10A wound around the substrate roller 101 is inserted between the backup roller 103 and the roll knife 104 and between the rollers 105A and 105B. Further, a wet laminate base material 10B wound around the base material roller 106 is inserted between the rollers 105A and 105B. And between these both base materials 10A and 10B, the polymer composition 120A is filled, and it becomes the polymer composition layer 10X. Both base materials 10A and 10B serve as a base for forming the polymer composition layer 10X in the form of a film, and also serve to isolate the polymer composition layer 10X from oxygen in the air.
  • the tray 102 is configured to store the polymer composition 120 ⁇ / b> A in the recess of the L-shaped member so that the polymer composition is in good contact with the peripheral surface side of the backup roller 103. Placed in. A sufficient amount of the polymer composition 120 ⁇ / b> A may be charged into the tray 102.
  • the tray 102 is not essential.
  • the tray 102 may be separately coated from the surface of the PET base material 10A conveyed to the downstream side from the roll knife 104. That is, any known coating method such as knife coating, blade coating, die coating, roll coating, curtain coating, or the like may be used instead of the coating method using the roll knife 104.
  • the backup roller 103 is rotatably supported and conveys the PET base material 10A that has been fed out to the rollers 105A and 105B when the apparatus is driven.
  • the roll knife 104 is formed with a blade portion having a sharp cross-sectional shape on the peripheral surface of the cylindrical body, and is disposed so that the blade portion faces the backup roller 103.
  • Each of the rollers 105A and 105B is a roller having the same configuration, and is disposed close to the backup roller 103 and the roll knife 104 with a narrower gap so that the thickness of the polymer composition layer can be adjusted. Yes. In addition, when the thickness adjustment can be sufficiently performed by the roll knife 104, the thickness adjustment may not be performed again by the rollers 105A and 105B.
  • Each gap between the backup roller 103 and the roll knife 104 and between the rollers 105A and 105B can be adjusted in a range of several ⁇ m or more and several hundreds ⁇ m or less in accordance with the thickness of the film to be formed.
  • ultraviolet rays are irradiated by the UV irradiation device 107.
  • the polymer composition forming the polymer composition layer 10X can be cured by ultraviolet irradiation to obtain a film-shaped resin molded body 10C.
  • the UV lamp used in the UV irradiation device 107 is not particularly limited, and a commercially available one (for example, an air-cooled mercury lamp manufactured by Eye Graphics Co., Ltd.) can be used.
  • the conditions for ultraviolet irradiation need to be appropriately adjusted depending on conditions such as the viscosity of the polymer composition to be cured.
  • the laminate film composed of the three-layer structure of the PET base material 10A, the film-like resin molded body 10C, and the wet laminate base material 10B obtained as described above is once wound up to form a laminate film roll 111. Also good.
  • the laminate film roll 111 may be subjected to (5) a substrate peeling treatment step and (6) a winding step described in FIG.
  • the polymer composition preparation step (2) the polymer composition coating step, (3) the wet laminating step, and (4) the curing step are performed as described above.
  • FIG. 2 is a schematic diagram illustrating an example of (5) a substrate peeling treatment process and (6) a winding process of the manufacturing method.
  • a laminate film having a three-layer structure is drawn out from the laminate film roll 111 obtained in the steps (1) to (4) and inserted between the peeling rollers 108A and 108B.
  • the laminate base material 10B is taken up by the take-up roller 109, and the PET base material 10A is taken up by the take-up roller 110, whereby the film-shaped resin molded body 10C and these base materials are peeled off to form a film.
  • the shaped resin molded body 10C can be obtained as a single layer.
  • the obtained film-shaped resin molded body 10 ⁇ / b> C may be subjected to a winding process and wound by the winding roller 112.
  • the resin molded body of the present invention can be manufactured by the manufacturing method described above.
  • Laminate The resin molded product of the present invention can be formed into a laminate by forming a gas barrier film on at least one surface. Such a laminate can be used for a display of an electronic device, and is particularly useful as a touch panel substrate.
  • the gas barrier film examples include an inorganic film such as a silicon oxide film or alumina, and an organic film made of a vinyl alcohol resin such as a polyvinyl alcohol resin or an ethylene-vinyl alcohol copolymer.
  • the inorganic film is preferably a silicon oxide film having a thickness of 0.01 to 0.1 ⁇ m, and the organic film is preferably an ethylene-vinyl alcohol copolymer having a thickness of 0.5 to 5 ⁇ m.
  • the resin molded body of the present invention can also be made into a laminate by forming a transparent conductive film on at least one surface.
  • a laminate can be used for a display of an electronic device, and is particularly useful as a touch panel substrate.
  • the transparent conductive film examples include inorganic films such as indium and tin oxide (ITO) and organic films such as poly (3,4-ethylenedioxythiophene) (PEDOT).
  • ITO indium and tin oxide
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • the resin molded product of the present invention is a polyfunctional urethane (meth) obtained by reacting a polyisocyanate compound (excluding those having an alicyclic structure) and a hydroxyl group-containing (meth) acrylate as the component (A). Since the polymerizable composition containing an acrylate and a bifunctional (meth) acrylate having an alicyclic structure as the component (B) is cured, the surface hardness is very high and moderate flexibility is exhibited. It has sufficient hardness and flexibility.
  • the laminate of the present invention using the above resin molded body also has a very high surface hardness, moderate flexibility, and has both sufficient hardness and flexibility. For this reason, the laminated body of this invention can be used suitably for a touchscreen or a flexible display.
  • Example 1 Component (A) was prepared. Specifically, 1,6-hexane diisocyanate isocyanurate type trimer (130 g) was prepared as a polyisocyanate compound. Moreover, dipentaerythritol pentaacrylate (870 g) was prepared as a hydroxyl group-containing (meth) acrylate. These, 0.8 g of hydroquinone methyl ether as a polymerization inhibitor, and toluene as a solvent were charged into a glass reactor equipped with a stirrer, a cooling tube, and a thermometer.
  • the —OH group / —NCO group of the isocyanurate type trimer of 1,6-hexane diisocyanate and dipentaerythritol pentaacrylate was 1/1. Furthermore, after adding 0.3 g of dibutyltin dilaurate as a urethanization catalyst and making it react at 85 degree
  • a trifunctional or higher polyfunctional polyester acrylate other than the components (A) and (B) was charged into a 677.6 g glass container.
  • the viscosity of the polymerizable composition was 2700 mPa ⁇ s. *
  • the obtained polymerizable composition is coated with a bar coater manufactured by Tester Sangyo Co., Ltd., ROD # 200 on an untreated surface (surface on which an easy adhesion layer is not formed) of A4100 (manufactured by Toyobo Co., Ltd.), which is a PET film. Applied. Another sheet of A4100 was prepared, and laminated so that the untreated surface of A4100 was in contact with the applied polymerizable composition to prepare a laminate film having a three-layer structure.
  • the polymerizable composition is cured by irradiating the laminate film with ultraviolet rays having an integrated irradiation amount of 1597 mJ / cm 2 using an ultraviolet curing device (trade name: CV-110Q-G manufactured by Fusion UV Systems Japan Co., Ltd.)
  • the PET films on both sides were peeled to prepare a resin molded body having a thickness of 258 ⁇ m.
  • Example 2 In the same manner as in Example 1, except that polyfunctional urethane (meth) acrylate obtained by reacting 150 g of 1,6-hexane diisocyanate trimer and 775 g of pentaerythritol triacrylate was used as component (A). Of 262 ⁇ m was prepared.
  • Comparative Example 1 A resin molded body having a thickness of 259 ⁇ m was prepared in the same manner as in Example 1 except that a polyfunctional acrylate obtained by reacting 176 g of isophorone diisocyanate and 825 g of pentaerythritol triacrylate was used as the component (A).
  • the polymerizable composition was measured at a rotational speed of 60 ppmm (No. 4 rotor) using a B-type viscometer “TVB-10” manufactured by Toki Sangyo Co., Ltd. under the condition of a viscosity of 20 ° C.
  • Optical properties (transmittance Tt, refractive index) Based on JIS K7361, it was measured using a turbidimeter (NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.).
  • Table 1 shows the measurement results.
  • the resin molded bodies of Examples 1 and 2 had a very high surface hardness and moderate flexibility, and had both sufficient hardness and flexibility.
  • the resin molded body of Comparative Example 1 uses a polyisocyanate compound having an alicyclic structure as the polyisocyanate compound constituting the component (A), the pencil hardness is inferior to 7H, which is sufficient. It did not have both hardness and flexibility.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)

Abstract

　La présente invention concerne : un article moulé en résine possédant une dureté de surface extrêmement élevée, présentant une flexibilité appropriée, et étant pourvu à la fois d'une dureté et d'une souplesse adéquate; et un corps stratifié qui utilise l'article moulé en résine. La présente invention concerne spécifiquement un article moulé en résine obtenu par durcissement d'une composition polymérisable contenant des composants (A) et (B), le composant (A) étant un méthacrylate d'uréthane polyfonctionnel obtenu en mettant en réaction un composé polyisocyanate (n'ayant pas une structure alicyclique) avec un méthacrylate contenant un hydroxyle et le composant (B) étant un méthacrylate bifonctionnel possédant une structure alicyclique.
PCT/JP2014/070863 2014-03-26 2014-08-07 Article moulé en résine et corps stratifié l'utilisant WO2015145798A1 (fr)

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JP6536383B2 (ja) * 2015-11-30 2019-07-03 コニカミノルタ株式会社 タッチパネル装置
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JP2005255979A (ja) * 2004-02-10 2005-09-22 Daicel Ucb Co Ltd 活性エネルギー線硬化型樹脂組成物の硬化物
WO2008120525A1 (fr) * 2007-03-23 2008-10-09 Dic Corporation Composition pouvant durcir aux ultraviolets pour une couche intermédiaire de disque optique et disque optique
JP2008248069A (ja) * 2007-03-30 2008-10-16 Sanyo Chem Ind Ltd 活性エネルギー線硬化性ハードコート用樹脂組成物
JP2009062423A (ja) * 2007-09-05 2009-03-26 Aica Kogyo Co Ltd 活性エネルギー線硬化型ハードコート樹脂組成物及びハードコートフィルム
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