WO2015008556A1 - Objet moulé en résine, plaque de protection et substrat d'écran tactile, tous deux pour des affichages, et procédé pour l'autoréparation d'un objet moulé en résine - Google Patents

Objet moulé en résine, plaque de protection et substrat d'écran tactile, tous deux pour des affichages, et procédé pour l'autoréparation d'un objet moulé en résine Download PDF

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Publication number
WO2015008556A1
WO2015008556A1 PCT/JP2014/065437 JP2014065437W WO2015008556A1 WO 2015008556 A1 WO2015008556 A1 WO 2015008556A1 JP 2014065437 W JP2014065437 W JP 2014065437W WO 2015008556 A1 WO2015008556 A1 WO 2015008556A1
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Prior art keywords
resin molded
molded body
meth
acrylate
molded article
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PCT/JP2014/065437
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English (en)
Japanese (ja)
Inventor
早川　誠一郎
由美子 山本
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日本合成化学工業株式会社
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Publication of WO2015008556A1 publication Critical patent/WO2015008556A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints

Definitions

  • the present invention relates to a resin molded product obtained by photocuring a photopolymerizable composition, and in particular, a sheet-shaped or film-shaped resin molded product having excellent optical characteristics, thermal characteristics, and mechanical characteristics.
  • the present invention relates to a resin molded body useful as a resin substrate or a protective plate for a display.
  • a glass substrate is often used as a display substrate.
  • a chemically strengthened glass substrate having a thickness of about 0.5 to 2 mm is widely used as a protective plate.
  • a glass substrate having a thickness of about 0.2 to 1.1 mm is widely used.
  • a glass substrate having a thickness of about 0.2 to 0.7 mm is widely used in liquid crystal displays and organic electroluminescence (organic EL) displays.
  • resin substrates have begun to be used from the viewpoint of weight reduction and safety and for the purpose of manufacturing flexible displays.
  • PMMA polymethyl methacrylate
  • PET polyethylene terephthalate
  • Such resin substrates have not only optical performance such as light transmittance and birefringence, but also thermal properties such as heat resistance and linear expansion coefficient, mechanical properties such as surface hardness and flexural modulus, water absorption and specific gravity, and resistance to resistance. High processability such as chemicals and solvent resistance is required.
  • a resin molded product obtained by photocuring a specific photopolymerizable composition can also be seen.
  • a photopolymerizable composition comprising a polyfunctional urethane (meth) acrylate having an alicyclic structure and a polyfunctional (meth) acrylate having an alicyclic structure gives a resin molded article having high pencil hardness.
  • a photopolymerizable composition comprising a monofunctional (meth) acrylate having an alicyclic structure, a polyfunctional urethane (meth) acrylate having an alicyclic structure, and a polyfunctional (meth) acrylate having an alicyclic structure has optical characteristics.
  • a resin molded body having excellent thermomechanical properties is provided (for example, see Patent Document 2).
  • a resin substrate having a high surface hardness enough to replace glass for example, a pencil hardness of 8H.
  • the pencil hardness of glass is 8H or more
  • the pencil hardness of glass whose surface is chemically strengthened is 9H or more.
  • the highest pencil hardness is 7H
  • the highest pencil hardness is 6H. That is, with these disclosed technologies, a resin substrate that is not easily damaged as much as glass and has a high hardness cannot be obtained.
  • the most commercially available pencil has the highest hardness of 10H.
  • the surface hardness of the substrate is insufficient, not only the final product is easily damaged, but also scratches and fine dents are generated during transportation and in the display device manufacturing process. In consideration of recent increases in display area and resolution, defects resulting from scratches and dents significantly impair the quality of the product. In addition, in the touch panel substrate, defects such as cracks and pinholes are likely to occur in the conductive film formed on the resin molded body. In order to improve the surface hardness, a method of hard-coating the surface of the resin molded body is generally used. However, a resin molded body that is easily charged tends to adhere foreign matter, and it is extremely difficult to eliminate foreign matter defects on the coated surface. It is. Multi-layering with a hard coat or protective film leads to an increase in cost.
  • the surface smoothness of the substrate greatly affects the light emission characteristics and device life.
  • the surface hardness of the substrate is particularly important because minute dents and protrusions due to scratches and foreign matters cause deterioration of the element and display defects such as black spots. Further, if the surface hardness is insufficient, a minute surface roughness occurs when an electrode or an organic EL layer is formed on the substrate, and sufficient light emission characteristics cannot be obtained. In order to achieve high brightness and low power consumption, it is necessary to improve the surface hardness of the resin substrate.
  • the surface hardness is particularly problematic. That is, when the surface hardness is low, the scratches with the transport roll and the scratches between the films in the winding process increase.
  • methods such as hard coat treatment, affixing a protective film, and inserting slip sheets are conceivable. However, these methods cause cost increase, so these treatments It is preferable to increase the surface hardness of the resin molded body and to be wound around the core material without any process.
  • a resin molded body that is lightweight and safe and suitable for a flexible display, in particular, has a very high surface hardness, and has self-repairing property against unevenness such as scratches. It aims at providing the resin molding which has.
  • the resin molded body having a pencil hardness equal to or higher than that of glass and having a decrease in haze with time even in a predetermined scratch resistance test is high in hardness, and the scratches on the surface of the resin are
  • the present invention was completed by finding that the resin molded body disappears due to self-healing properties.
  • the gist of the present invention is that a transparent resin molded body having a thickness of 0.5 mm or more obtained by photocuring the photopolymerizable composition [I] satisfies the following requirements ( ⁇ ) and ( ⁇ ): It is related with the resin molding characterized by this.
  • the pencil hardness of the resin molded body surface is 8H or more.
  • ⁇ In a test in which a load of 160 g is applied to # 0000 steel wool having a diameter of 1 cm and reciprocated 5000 times at a stroke width of 5 cm and a speed of 5 cm / second, the haze immediately after the test is ⁇ 1 (%).
  • the haze ratio ( ⁇ 2 / ⁇ 1) is 0.9 or less when the haze after leaving for 3 days at 23 ° C. and 50% RH is ⁇ 2 (%).
  • the present invention provides a display protective plate made of the resin molded body, and further a touch panel substrate in which a transparent conductive film is formed on one surface of the resin molded body.
  • the present invention also provides a self-repairing method for a resin molded body that repairs a scratch generated in the resin molded body.
  • the resin molded body of the present invention is excellent in optical characteristics, thermal characteristics, and mechanical characteristics, has a particularly high surface hardness, and can be a resin molded body suitable for a protective plate and a touch panel substrate. In particular, since it has self-healing properties, it is suitable as a substrate located in the outermost layer of the display.
  • (meth) acrylate is a general term for acrylate and methacrylate.
  • the resin molded body of the present invention satisfies the above requirements ( ⁇ ) and ( ⁇ ) in a transparent resin molded body having a thickness of 0.5 mm or more obtained by photocuring the photopolymerizable composition [I]. Is.
  • the resin molded body of the present invention has a relatively thick thickness of 0.5 mm or more, preferably 0.5 to 5 mm, more preferably 0.6 to 4 mm, still more preferably 0.6 to 3 mm. Particularly preferred is 0.7 to 2 mm, and particularly preferred is 0.7 to 1 mm. If the thickness is too thin, the rigidity as a display substrate or a protective plate tends to be inferior, and if it is too thick, the display tends to be thick and heavy.
  • the pencil hardness of the surface of the resin molded body of the present invention is preferably as high as possible considering glass substitution.
  • the pencil hardness is 8H or more, more preferably 9H or more, and particularly preferably 10H or more.
  • the surface hardness is higher. preferable.
  • the pencil hardness is evaluated in accordance with JIS K-5600-5-4 under a load of 750 g, immediately after rubbing the pencil and immediately after rubbing the pencil at 23 ° C., 50% RH. Then, the scratches on the surface after standing for 3 days are evaluated visually, and the pencil hardness without scratches is measured.
  • the thickness of the resin molded body obtained by photocuring is more difficult to produce, and the internal reaction rate is low in the thickness direction, and accordingly it is difficult to increase the surface hardness.
  • the present invention even if it is thick, a high surface hardness could be achieved, and an unprecedented resin molded body could be obtained.
  • the resin molding has a decrease in the haze with time in a predetermined scratch resistance test.
  • the haze immediately after the test is ⁇ 1 (%).
  • the resin molded body of the present invention has a haze ratio ( ⁇ 2 / ⁇ 1) of 0.9 or less. It can be confirmed that the scratches that have entered the surface of the resin molded body have disappeared due to the self-repairing property of the resin.
  • the preferable range of the haze ratio ( ⁇ 2 / ⁇ 1) is 0.8 or less, more preferably 0.7 or less, and particularly preferably 0.6 or less. When the haze ratio ( ⁇ 2 / ⁇ 1) exceeds 0.9, the self-repairing property tends to be low.
  • the self-repairing property as used herein means the ability to fill a scratch or dent by movement of the resin component even if the surface of the resin molded body has a scratch or a dent.
  • rubbery materials have the ability to repair dents, but it is very difficult to develop such a capability with a hard and transparent resin molding.
  • urethane-based coating agents have a self-healing ability of scratches, but these are related to coating agents, and it is difficult to express such self-repairing ability with a relatively thick resin molding.
  • the light transmittance is preferably 85% or more, particularly 88% or more, more preferably 90% or more, from the viewpoint of increasing the brightness or definition of the display. preferable. If the light transmittance is too small, the brightness of the display tends to decrease. The upper limit of the light transmittance is usually 99%.
  • the light transmittance (%) is the total light transmittance measured according to JIS K 7375.
  • the haze of the resin molded body of the present invention is preferably 1% or less, particularly 0.7% or less, more preferably 0. It is preferable that it is 5% or less. If the haze is too large, the definition of the display tends to decrease. The lower limit of haze is usually 0.001%.
  • haze is a value measured according to JIS K 7136.
  • the resin molded body of the present invention preferably has a surface roughness Ra of at least one surface of 20 nm or less, particularly 15 nm or less, more preferably 10 nm or less from the viewpoint of display quality of the display. If the surface roughness is too large, the quality of the display tends to deteriorate.
  • the lower limit value of the surface roughness Ra is usually 1 nm. In the present invention, the surface roughness Ra is measured based on JIS B0601: 2001.
  • the resin molded body of the present invention preferably has a flexural modulus of 3 GPa or more (25 ° C.), particularly 3 to 5 GPa from the viewpoint of thinning the display. If the flexural modulus is too small, the toughness of the resin molded product tends to decrease, and the display tends to bend or swell. In addition, when a bending elastic modulus is too large, there exists a tendency for manufacture of a flexible display to become difficult.
  • the resin molded body of the present invention preferably has a glass transition temperature of 200 ° C. or higher, more preferably 210 ° C. or higher, and particularly preferably 220 ° C. or higher from the viewpoint of display reliability.
  • the upper limit of the glass transition temperature is 400 ° C.
  • the glass transition temperature is a value measured according to JIS K 7244.
  • the resin molded body of the present invention preferably has a saturated water absorption of 0.5 to 2%, particularly 0.8 to 1.7%, more preferably 1 to 1.5%. If the saturated water absorption is too small, the self-repairing property tends to be lowered, and if it is too much, the substrate tends to be warped or swelled.
  • the photopolymerizable composition in satisfying the above various physical properties, it can be obtained by photocuring the photopolymerizable composition.
  • the photopolymerizable composition the following components (A), (B), and (C It is preferable to use a photopolymerizable composition [I] containing).
  • the content ratio (A: B) of the component (A) and the component (B) is preferably 30:70 to 60:40 in terms of weight ratio in view of good balance of physical properties such as surface hardness and saturated water absorption. .
  • polyfunctional here means having two or more (meth) acryloyl groups in a molecule
  • Component (A) is a urethane (meth) acrylate containing two or more (meth) acryloyl groups in the molecule. Since it is polyfunctional, the curing rate is improved, and a resin molded product can be obtained with high productivity. Moreover, a crosslinked resin can be formed by photocuring, and a resin molding with high surface hardness can be obtained. It should be noted that component (A) has a urethane group in the molecule and exhibits self-healing properties. The reason for this is not clear, but it is presumed that the molecular chains broken by the scratches recombine due to hydrogen bonding. In addition, a flexible resin molded article excellent in mechanical strength such as bending elastic modulus and impact resistance can be obtained by the hydrogen bond.
  • component (A) has an alicyclic structure in the molecule, and the water absorption rate of the resin molded product is reduced by this alicyclic structure.
  • component (B) is also a polyfunctional (meth) acrylate, a highly heat-resistant resin molded product is provided. Although the effect of improving heat resistance is greater than that of the component (A) urethane (meth) acrylate, this monomer alone is too brittle because it becomes a glass-like crosslinked resin. In addition to surface hardness and self-healing property, heat resistance and flexibility are achieved by containing and copolymerizing component (A) urethane (meth) acrylate and component (B) polyfunctional (meth) acrylate. Can be obtained.
  • component (B) is preferably bifunctional and more preferably methacrylate.
  • the component (B) also has an alicyclic structure, and this alicyclic structure also reduces the saturated water absorption rate of the resin molded body.
  • the content ratio (A: B) of component (A) and component (B) is preferably 30:70 to 60:40 (weight ratio). If the amount of component (A) is too small, surface hardness and self-healing properties tend to decrease. Conversely, if the amount of component (A) is too large, it becomes difficult to produce a resin molded product because of high viscosity, and Saturated water absorption tends to increase.
  • a preferable range of the content ratio is 35:65 to 55:45 (weight ratio), and particularly preferably 40:60 to 50:50 (weight ratio).
  • the photopolymerizable composition [I] of the present invention preferably has a viscosity at 23 ° C. of 1 to 5 Pa ⁇ s. More preferably, it is 2 to 4 Pa ⁇ s, and still more preferably 2 to 3 Pa ⁇ s. If the viscosity is too low, unpolymerized monomers tend to remain in the molding step, and conversely, if too high, handling tends to be difficult. Examples of the method for adjusting the viscosity include appropriately controlling the types and blending amounts of the components (A) and (B).
  • 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 1000. When the number average molecular weight is too small, curing shrinkage increases and birefringence tends to occur. On the other hand, if it is too large, the crosslinkability tends to decrease and the heat resistance tends to decrease.
  • the number average molecular weight is measured as follows. That is, the number average molecular weight (Mn) is a number average molecular weight in terms of standard polystyrene molecular weight, and can be measured by high performance liquid chromatography (“Waters 2695 (main body)” and “Waters 2414 (detector)” manufactured by Nippon Waters).
  • the polyfunctional urethane (meth) acrylate having an alicyclic structure as the component (A) is prepared by using a polyisocyanate compound having an alicyclic structure and a hydroxyl group-containing (meth) acrylate, if necessary, using a catalyst such as dibutyltin dilaurate. It can be obtained by reacting.
  • polyisocyanate compound having an alicyclic structure examples include, for example, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, hydrogenated xyly
  • examples include a diisocyanate, a hydrogenated diphenylmethane diisocyanate, and a trimer compound of isophorone diisocyanate. Of these, isophorone diisocyanate is preferred in terms of self-healing properties.
  • hydroxyl group-containing (meth) acrylate examples include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3- (meth) Examples include acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tri (meth) acrylate.
  • pentaerythritol tri (meth) acrylate dipentaerythritol penta (meth) acrylate, and dipentaerythritol tri (meth) acrylate are preferable in terms of surface hardness.
  • Two or more polyfunctional urethane (meth) acrylates obtained by a reaction between a polyisocyanate compound having an alicyclic structure and a hydroxyl group-containing (meth) acrylate may be used in combination.
  • these polyfunctional urethane (meth) acrylates acrylate is preferable from the viewpoint of curing speed, tetrafunctional or higher is more preferable from the viewpoint of heat resistance, and from the viewpoint of surface hardness, it is represented by the following formulas (1) to (4).
  • Particularly preferred is a tetrafunctional or higher functional urethane acrylate having an alicyclic structure.
  • the upper limit of polyfunctionality is usually 18, preferably 6 functionalities.
  • pentadecane di (meth) acrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ]
  • pentadecane di (meth) acrylate, bis (hydroxy) pentacycle [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ]
  • pentadecane acrylate methacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 3,6 . 0 2,7 .
  • 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) ) Trifunctional (meth) acrylates such as cyclohexane and 1,3,5-tris (methacryloyloxyethyloxymethyl) cyclohexane.
  • bifunctional (meth) acrylates are preferred from the viewpoint of flexibility.
  • more preferred difunctional methacrylate from the viewpoint of heat resistance.
  • at least one bifunctional (meth) acrylate selected from the group consisting of the following general formulas (5), (6) and (7) is preferable from the viewpoint of optical performance, and bifunctional methacrylate is particularly preferable.
  • Component (C) is a photopolymerization initiator such as benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6. -Trimethylbenzoyldiphenylphosphine oxide and the like.
  • radical cleavage type photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable from the viewpoint of rapid curing.
  • photopolymerization initiators (C) may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (C) is 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, particularly 100 parts by weight in total of the component (A) and the component (B).
  • the amount is preferably 0.3 to 2 parts by weight, particularly 0.5 to 1.5 parts by weight.
  • auxiliary components may be included as long as the physical properties of the resin molded body of the present invention are not impaired.
  • monomers having an ethylenically unsaturated bond other than components (A) and (B) may be included as long as the physical properties of the resin molded body of the present invention are not impaired.
  • monomers having an ethylenically unsaturated bond other than components (A) and (B) may be included as long as the physical properties of the resin molded body of the present invention are not impaired.
  • monomers having an ethylenically unsaturated bond other than components (A) and (B) include polymerization inhibitors, thermal polymerization initiators, chain transfer agents, antioxidants, ultraviolet absorbers, antifoaming agents, leveling agents , Blueing agents, dyes and pigments, fillers and the like.
  • Examples of the monomer having an ethylenically unsaturated bond other than components (A) and (B) include methyl methacrylate, 2-hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and 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) acrylate
  • Polyfunctional (meth) acrylates such as loxypropane, 2,2-bis [4- (meth) acryloyloxyphenyl] propane, trimethylolpropane tri (meth) acrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and the like ( Examples include methacrylic acid derivatives, styrene compounds such as s
  • the content of the monomer having an ethylenically unsaturated bond other than components (A) and (B) is 30 parts by weight or less with respect to a total of 100 parts by weight of component (A) and component (B), It is preferably 20 parts by weight or less, particularly 10 parts by weight or less. When there is too much content, it exists in the tendency for the heat resistance and impact resistance of a resin molding to fall.
  • 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
  • Peroxyesters such as dialkyl peroxides such as oxides, peroxyesters such as t-butylperoxybenzoate and t-butylperoxy (2-ethylhexanoate), diacyl peroxides such as benzoyl peroxide, and peroxys such as diisopropylperoxycarbonate
  • peroxides such as carbonate, peroxyketal, and ketone peroxide.
  • a polyfunctional mercaptan compound is preferable.
  • the polyfunctional mercaptan compound include pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, and the like. These polyfunctional mercaptan compounds are preferably used in a proportion of usually 10 parts by weight or less, more preferably 5 parts by weight or less, particularly 3 parts by weight with respect to 100 parts by weight of the photopolymerizable composition [I]. Part or less is preferred. When there is too much this usage-amount, there exists a tendency for the heat resistance and rigidity of the resin molding obtained to fall.
  • antioxidants examples include 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol, and 2,6-di- t-butyl-4-s-butylphenol, 2,6-di-t-butyl-4-hydroxymethylphenol, n-octadecyl- ⁇ - (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) ) Propionate, 2,6-di-t-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 2,4 -Bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di-t-butylanilino) -1,3,5-triazine, 4,4-methylene-bis (2,6-di-)
  • the content of the antioxidant is usually preferably 0.001 to 1 part by weight, particularly preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the photopolymerizable composition [I]. is there. If the amount of such an antioxidant is too small, the light resistance of the resin molded product tends to decrease, and if it is too large, the light transmittance tends to decrease.
  • the photopolymerizable composition [I] used in the present invention is obtained.
  • the manufacturing method of the resin molding of this invention using this photopolymerizable composition [I] is demonstrated.
  • the photopolymerizable composition [I] is preferably photocured using an ultraviolet ray having a wavelength of 200 to 400 nm at an irradiation light amount of 1 to 100 J / cm 2 or less.
  • a more preferable range of the irradiation light amount is 5 to 50 J / cm 2 , and further preferably 10 to 30 J / cm 2 .
  • Illuminance of ultraviolet rays 10 ⁇ 5000mW / cm 2, and particularly preferably from 100 ⁇ 1000mW / cm 2. If the illuminance is too small, there is a tendency that the resin molded body is not sufficiently cured. Conversely, if the illuminance is too large, polymerization tends to run away and birefringence tends to increase.
  • the ultraviolet ray source may be any one that is usually used in photopolymerization, and examples thereof include a metal halide lamp, a high-pressure mercury lamp lamp, an electrodeless mercury lamp, and an LED lamp.
  • a metal halide lamp In order to prevent polymerization from running away due to infrared rays generated from a light source, it is also possible to use a filter that blocks infrared rays, a mirror that does not reflect infrared rays, or the like for the lamp.
  • the resin molded body obtained in the present invention is preferably heat-treated for improving the degree of polymerization or releasing stress strain, and it is particularly preferred to heat-treat at 100 ° C. or higher.
  • photoforming is performed batchwise. That is, a mold in which two transparent glasses are opposed to each other through a spacer for controlling the thickness is produced, the photopolymerizable composition [I] is injected into the cavity, and the active energy ray is irradiated and cured. And demolding.
  • the resin molded body of the present invention can be obtained.
  • the photopolymerizable property is obtained.
  • the content ratio of the component (A) polyfunctional urethane (meth) acrylate and the component (B) polyfunctional (meth) acrylate in the composition [I] is important, and in the case of a thick resin molding, the component (A ) In a relatively large amount, the resin molded product of the present invention can be obtained efficiently.
  • the reaction rate by photopolymerization is high when the thickness of the resin molded product is thin, the surface hardness (for example, 6H to 7H) is low even if the content ratio of the polyfunctional urethane (meth) acrylate is small or large.
  • the content ratio of the polyfunctional urethane (meth) acrylate is very important.
  • the resin molding of this invention although it has a self-repairing property with respect to the damage
  • the resin molded body is preferably heat-treated at 50 to 300 ° C., preferably 100 to 250 ° C. in the air or under vacuum. The reason that self-healing is accelerated by heating is presumed to be because the polymer in the scratches and dents easily moves.
  • examples of the contact method include immersion, shower, steam and the like, but immersion is preferred from the viewpoint of simplicity of equipment.
  • solvent solvents such as water, alcohols such as methanol, ethanol and propanol, toluene, xylene, methyl ethyl ketone, methylene chloride, chloroform, DMSO and DMF are used.
  • immersion in a solvent the resin molded body is preferably immersed in the solvent for several hours to several days, preferably for 1 hour to 3 days.
  • the immersion temperature is preferably room temperature to 200 ° C., particularly 50 to 100 ° C. The reason why the self-repair is accelerated by the immersion in the solvent is presumed to be that the polymer easily moves due to the swelling of the surface layer of the scratch or the dent.
  • a gas barrier film can be formed on the resin molded body of the present invention.
  • the gas barrier film include inorganic films such as a silicon oxide film and alumina, and organic films made of a vinyl alcohol resin such as a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer.
  • the inorganic film is preferably a silicon oxide film having a thickness of 0.05 to 0.5 ⁇ 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 be formed as a touch panel substrate by forming a transparent conductive film on one side.
  • the material of the transparent electrode is not particularly limited, and examples thereof include inorganic conductive films such as ITO and IGZO, and organic conductive films such as PEDOT.
  • the surface resistance value of the transparent conductive film is preferably 1000 ⁇ / ⁇ or less, more preferably 10 to 900 ⁇ / ⁇ or less, and still more preferably 50 to 500 ⁇ / ⁇ or less. If the surface resistance is too high, the conductivity tends to decrease.
  • the resin molded body of the present invention can be formed as a protective plate with an adhesive layer by forming an adhesive layer on one side.
  • the material of the pressure-sensitive adhesive layer is not particularly limited, and an acrylic or silicon-based pressure-sensitive adhesive is appropriately used.
  • the resin molded body of the present invention can be suitably used particularly as a protective plate or a touch panel substrate.
  • Pencil hardness The test was conducted under a load of 750 g according to JIS K-5600-5-4. Immediately after rubbing the pencil and after rubbing, the scratches on the surface after standing at 23 ° C. and 50% RH for 3 days were visually evaluated, and the pencil hardness without scratches was measured.
  • the obtained resin molding had favorable characteristics as a substrate as shown in Table 2 below. In particular, it was 8H in the visual evaluation immediately after rubbing with a pencil, but it was 9H in the visual evaluation after standing at 23 ° C. and 50% RH for 3 days, and self-repairability was also confirmed. Self-healing properties were also confirmed in haze evaluation (haze ratio ( ⁇ 2 / ⁇ 1)).
  • a transparent conductive film made of ITO having a thickness of 500 mm (angstrom) was formed on one surface of the obtained resin molding by sputtering to obtain a touch panel substrate.
  • Such a touch panel substrate had a surface resistance value of 100 ⁇ / ⁇ , and had good characteristics as a touch panel substrate.
  • the surface hardness is very excellent, and also the self-healing from the measurement result of the haze ratio ( ⁇ 2 / ⁇ 1) It has excellent properties.
  • the comparative example 1 since there was too little polyfunctional urethane (meth) acrylate (A), it was inferior to the surface hardness and self-repairing property of a resin molding.
  • the photopolymerizable composition [I] was the same as in Example 1, but it was a thin resin molded product, so that deep scratches were likely to occur in a heavy load scratch resistance test (500 g). It was also inferior to scratching and self-healing.
  • the resin molded body of the present invention can be advantageously used for various optical materials and electronic materials.
  • liquid crystal substrates, organic / inorganic EL substrates, electronic paper substrates, light guide plates, phase difference plates, touch panels, etc. various display members, optical recording substrates and film / coating applications for optical disks, thin films, etc.
  • It can be used for energy applications such as battery substrates and solar cell substrates, optical communication applications such as optical waveguides, and various optical films, sheets and coatings such as functional films and sheets, antireflection films and optical multilayer films.
  • it is highly expected as a capacitive touch panel substrate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un objet transparent moulé en résine présentant une épaisseur de 0,5 mm ou plus qui est produit par photodurcissement d'une composition photopolymérisable [I] et qui satisfait aux exigences (α) et (β) mentionnées ci-dessous. Il devient ainsi possible d'obtenir : un objet moulé en résine qui présente un poids léger, qui est sûr et qui convient pour un affichage souple, en particulier un objet moulé en résine présentant une dureté de surface extrêmement élevée et présentant également une propriété d'autoréparation lorsque des inégalités, telles que des rayures, se trouvent sur l'objet moulé en résine. (α) La dureté au crayon de la surface de l'objet moulé en résine est de 8H ou plus ; et (β) dans un test tel qu'une charge de 160 g est appliquée sur une laine d'acier #0000 présentant un diamètre de 1 cm contre l'objet moulé en résine, puis la laine d'acier est déplacée 5000 fois vers l'avant et vers l'arrière sur une largeur de course de 5 cm et à une vitesse de 5 cm/sec., le taux de voile (β2/β1) est de 0,9 ou moins, β1 (%) représentant la valeur de voile donnée immédiatement après le test et β2 (%) représentant la valeur de voile donnée après avoir permis à l'objet moulé en résine de rester pendant 3 jours et à 23°C et à une humidité relative de 50% après le test.
PCT/JP2014/065437 2013-07-18 2014-06-11 Objet moulé en résine, plaque de protection et substrat d'écran tactile, tous deux pour des affichages, et procédé pour l'autoréparation d'un objet moulé en résine WO2015008556A1 (fr)

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JP2013149394 2013-07-18

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JP2016176012A (ja) * 2015-03-20 2016-10-06 日本合成化学工業株式会社 ラジカル硬化性組成物、プラスチックシート、プラスチックシートロール及び成形物
JPWO2016159023A1 (ja) * 2015-03-31 2017-07-13 Jnc株式会社 コーティング剤、皮膜、積層体、表面保護物品
WO2017216592A3 (fr) * 2016-06-15 2018-03-15 Hungaro Lux Light Kft Film antireflet et son utilisation sur un substrat
WO2021192789A1 (fr) * 2020-03-23 2021-09-30 東洋紡株式会社 Stratifié

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KR101862252B1 (ko) * 2015-08-03 2018-05-29 주식회사 엘지화학 플렉시블 플라스틱 필름
KR102094450B1 (ko) 2015-08-03 2020-03-27 주식회사 엘지화학 플렉시블 플라스틱 필름
TWI821234B (zh) 2018-01-09 2023-11-11 美商康寧公司 具光改變特徵之塗覆製品及用於製造彼等之方法
CN110563899B (zh) * 2019-08-19 2022-03-08 武汉华星光电半导体显示技术有限公司 聚合物及其制备方法以及显示装置
US20220011478A1 (en) 2020-07-09 2022-01-13 Corning Incorporated Textured region of a substrate to reduce specular reflectance incorporating surface features with an elliptical perimeter or segments thereof, and method of making the same

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JPWO2016159023A1 (ja) * 2015-03-31 2017-07-13 Jnc株式会社 コーティング剤、皮膜、積層体、表面保護物品
WO2017216592A3 (fr) * 2016-06-15 2018-03-15 Hungaro Lux Light Kft Film antireflet et son utilisation sur un substrat
US11029514B2 (en) 2016-06-15 2021-06-08 Hungaro Lux Light Kft. Antireflection film and its use on a substrate
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