WO2012096111A1 - ラジカル硬化性ホットメルトウレタン樹脂組成物、及び光学用成形体 - Google Patents
ラジカル硬化性ホットメルトウレタン樹脂組成物、及び光学用成形体 Download PDFInfo
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- WO2012096111A1 WO2012096111A1 PCT/JP2011/079626 JP2011079626W WO2012096111A1 WO 2012096111 A1 WO2012096111 A1 WO 2012096111A1 JP 2011079626 W JP2011079626 W JP 2011079626W WO 2012096111 A1 WO2012096111 A1 WO 2012096111A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
- C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
Definitions
- the present invention relates to a radical curable hot melt urethane resin composition and an optical molded body using the same. More specifically, “hot melt property” that is in a heated and melted state at the time of application but fast cooling and solidification after application, for example, infrared rays, visible rays, ultraviolet rays, X rays, electron beams, ⁇ rays, ⁇ rays, ⁇ rays, Radical curable hot-melt urethane resin composition that has two characteristics of “fast curing” by irradiation of active energy rays such as sunlight.
- “hot melt property” that is in a heated and melted state at the time of application but fast cooling and solidification after application, for example, infrared rays, visible rays, ultraviolet rays, X rays, electron beams, ⁇ rays, ⁇ rays, ⁇ rays, Radical curable hot-melt urethane resin composition that has two characteristics of “fast curing”
- the present invention relates to a body (for example, a light guide article such as a light guide film, a light guide sheet, a protective film, a key sheet film, an optical film, a light guide plate).
- a body for example, a light guide article such as a light guide film, a light guide sheet, a protective film, a key sheet film, an optical film, a light guide plate.
- reactive hot melt urethane is being used as a high-value-added product to replace solvent-based resins and water-based resins for a wide range of applications including, for example, adhesives for building materials and fibers, as well as coating agents.
- reactive hot melt urethane is that it is solid at room temperature and melts into a liquid or viscous property when it is heated, and "hot melt property” is a property that develops cohesive force again by cooling, It has both “humidity curable” that provides adhesiveness due to the formation of a cross-linked structure resulting from the reaction between moisture (water) in the air and isocyanate groups, and has attracted attention from various fields as a solvent-free method. Has been expanding its demand. In the present invention, moisture (water) and water vapor are treated as consent.
- a reactive hot melt urethane for example, a hot melt urethane prepolymer having an isocyanate group at the terminal (hereinafter also referred to as “isocyanate group-terminated hot melt urethane prepolymer” or “urethane prepolymer”) was used. Things are typically known.
- radical curable resins Compositions are known and have been put to practical use in a wide range of applications such as adhesives, printing inks, films, sheets, or paints such as plastic, paper, and woodwork.
- the radical curable resin composition includes (1) fast curing (fast curability) and high productivity, (2) low pollution and environment-friendly type without organic solvent, (3 ) Since there is no need to heat cure, there are many advantages such as almost no adverse effects (deterioration, deformation, discoloration, etc.) due to heat on the base material, and (4) energy cost can be reduced.
- a radical curable resin composition for example, an unsaturated acrylic resin, a polyester acrylate resin, a urethane acrylate resin, an epoxy acrylate resin, a polyene-polythiol addition polymerization resin, a cationic polymerization resin, an unsaturated polyester resin, or the like was used.
- urethane acrylate resins are generally used in a relatively large amount because they are excellent in rapid curability and have a large degree of freedom in resin design.
- a polyisocyanate compound having two or more isocyanate groups per molecule, a polyester polyol or polytetramethylene ether glycol, a trihydric or higher polyhydric alcohol, and a hydroxyl group-containing (meth) acrylate are reacted.
- a photocurable resin composition containing a urethane (meth) acrylate resin having a (meth) acryloyl group and an isocyanate group at a terminal and a photopolymerization initiator obtained by the process for example, Patent Document 1 and 2).
- Such a photocurable resin composition is said to be rapidly cured by irradiation with light such as ultraviolet rays, to have good gloss and adhesion, and to have good crack resistance of the resulting coating film.
- the photocurable resin compositions obtained in Patent Documents 1 and 2 have characteristics such as durability (particularly hydrolysis resistance) and yellowing resistance when a cured product obtained by light irradiation is used for a long period of time. There was a problem in practical use.
- a (meth) acrylate reactive oligomer having a alicyclic structure in the molecule a (meth) acrylate polymer, an epoxy (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer and an unsaturated polyester oligomer
- a radical curable resin composition containing at least one selected polymer or oligomer and a polymerizable monomer is known (see, for example, Patent Document 3).
- Such a radically curable resin composition has low shrinkage, does not deteriorate the surface of the molded product, and does not impair transparency.
- the radical curable resin composition described in Patent Document 3 has physical properties such as demolding property, elongation and flexibility of the molded product as well as production problems that the curing time is too long and the energy cost is excessively high. There was a performance problem that it was very inferior.
- optical molded bodies such as a light guide film, a light guide sheet, a protective film, a key sheet film, an optical film, a light guide plate, and a light guide fiber are being used in various applications as optical molded bodies.
- the general required performance required for the optical molded body is not only to have heat resistance and transparency, but also handling when performing various processing using the optical molded body. From the viewpoint of safety, good flexibility is required.
- the viscosity average molecular weight is 1.0 ⁇ 10 4 to 1.5 ⁇ 10 4
- the content of low molecular weight components having a molecular weight of 1000 or less is 1.5% by weight or less
- total nitrogen A glycerin monoester type release agent is added in an amount of 0.01 to 100 parts by weight of an aromatic polycarbonate resin having a content of 15 ppm or less, a Cl content of 100 ppm or less, and an OH end group content of 0.1 to 30 eq / ton.
- An aromatic polycarbonate resin composition for a light guide plate containing -0.3 parts by weight is known (see, for example, Patent Document 4).
- Such an aromatic polycarbonate resin composition for a light guide plate has good heat resistance and moldability, does not cause discoloration even with a thin molded product, and has good transparency and strength.
- the light guide plate obtained using the aromatic polycarbonate resin composition described in Patent Document 4 is relatively good in transparency and heat resistance, but is too hard and inferior in flexibility. There is a problem that the range of use is extremely limited.
- the object of the present invention is (1) solid, waxy or other semi-solid or viscous properties at normal temperature (20 ⁇ 15 ° C), but when heated, it melts into a liquid or viscous property.
- "Hot melt property” in which the cohesive force is instantly expressed again by cooling after application to the substrate, and (2) for example, infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, ⁇ rays, ⁇ rays, ⁇ rays It has two characteristics of "fast curing” by irradiation of active energy rays such as sunlight, moderate flexibility (low hardness), durability (especially hydrolysis resistance), LED (light emitting diode) light High transparency (light transmittance) to efficiently guide heat, thermal stability that does not cause deterioration, deformation, discoloration, etc.
- Isocyanate of an isocyanate group-terminated hot-melt urethane prepolymer which is a resin composition obtained by reacting an aliphatic polycarbonate polyol, an alicyclic polycarbonate polyol, or a polyol containing an aliphatic polyether polyol with an alicyclic polyisocyanate
- the product has two characteristics: excellent hot-melt property and fast curing by irradiation with active energy rays, moderate flexibility (low hardness), durability (especially hydrolysis resistance), LED (light emitting diode) High transparency to efficiently guide light (light transmittance), thermal stability that does not cause deteriorati
- the present invention is a radical curable hot melt urethane resin composition containing a hot melt urethane (X) having a (meth) acryloyl group and a radical polymerization initiator (Y), wherein the hot melt urethane (X ) Reacts the polyol (A) containing the aliphatic polycarbonate polyol (a1), the alicyclic polycarbonate polyol (a2), or the aliphatic polyether polyol (a3) with the alicyclic polyisocyanate (B).
- a hot melt urethane (X) having a (meth) acryloyl group and a radical polymerization initiator (Y)
- the hot melt urethane (X ) Reacts the polyol (A) containing the aliphatic polycarbonate polyol (a1), the alicyclic polycarbonate polyol (a2), or the aliphatic polyether polyol (a3) with the alicyclic polyiso
- C hot-melt urethane prepolymer
- D hot melt urethane
- Y radical polymerization initiator
- the present invention also provides an optical molded article produced using the radical curable hot melt urethane resin composition.
- the radical-curable hot-melt urethane resin composition of the present invention has a "hot-melt property" that is rapidly solidified by cooling after being applied to a substrate in a heated and melted state, for example, infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, It is a resin composition that has two characteristics of “fast curing” by irradiation of active energy rays such as ⁇ rays, ⁇ rays, ⁇ rays, sunlight, etc., and has moderate flexibility and durability (especially hydrolysis resistance) ), Transparency (light transmittance), thermal stability, yellowing resistance (non-yellowing), adhesion to the substrate, high productivity (fast curing), etc.
- a light guide film, a light guide sheet, a protective film, a key sheet film, an optical film, a light guide plate, an optical molded body such as a light guide fiber, or an adhesive, adhesive, coating agent for a film / sheet or fiber Useful for a wide range of light guide articles such as .
- the radical curable hot melt urethane resin composition of the present invention comprises a hot melt urethane (X) having a (meth) acryloyl group (hereinafter referred to as hot melt urethane (X)) and a radical polymerization initiator (Y). It is contained in an amount within the range.
- X hot melt urethane
- Y radical polymerization initiator
- the hot melt urethane (X) used in the present invention is the total number of isocyanate groups in the isocyanate group-terminated hot melt urethane prepolymer (C) obtained by reacting the polyol (A) with the alicyclic polyisocyanate (B). More than 50 mol% and not more than 100 mol%, preferably 60 to 100 mol%, more preferably 80 to 100 mol%, by the (meth) acrylate compound (D) having an active hydrogen-containing group (meth) acryloyl group Is introduced.
- the hot melt urethane (X) in such a range, moderate flexibility, quick curability, shape retention after application to the substrate, mechanical strength, durability (especially water resistance) Degradability) and excellent performance such as adhesion to a substrate (particularly adhesion to metal) can be exhibited.
- radical polymerization initiator (Y) used in the present invention known ones can be used, and examples thereof include a photopolymerization initiator and a peroxide. From the viewpoint of productivity, a photopolymerization initiator is preferable. Details will be described later.
- a polyol having no aromatic cyclic structure is used as the polyol (A) because yellow resistance and transparency can be improved.
- the polyol (A) include aliphatic polycarbonate polyols, alicyclic polycarbonate polyols, aliphatic polyether polyols, alicyclic polyester polyols, and aliphatic polyester polyols, and more preferable aliphatic polycarbonate polyols. , Alicyclic polycarbonate polyol, aliphatic polyether polyol, and alicyclic polyester polyol.
- Examples of the aliphatic polycarbonate polyol (a1) or alicyclic polycarbonate polyol (a2) that can be used for the polyol (A) include those obtained by reacting, for example, a carbonate and / or phosgene with a polyol described later. It is done.
- Examples of the carbonate ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, and diphenyl carbonate.
- polyol capable of reacting with the carbonate ester or phosgene examples include, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, and tripropylene glycol.
- the aliphatic polycarbonate polyol (a1) or the alicyclic polycarbonate polyol (a2) is, for example, 1,4-butanediol, 1,5 from the viewpoint of further improving the transparency of the optical molded article.
- -Preferred is one obtained by reacting a polyol containing at least one selected from pentanediol and 1,6-hexanediol with a dialkyl carbonate.
- aliphatic polycarbonate polyol (a1) or alicyclic polycarbonate polyol (a2) a polycarbonate polyol having an alicyclic structure is used from the viewpoint of maintaining good transparency and improving initial cohesion. Is preferred.
- alicyclic polycarbonate polyol what is obtained, for example by making the polyol containing at least 1 type chosen from a cyclohexane dimethanol and its derivative (s) and a dialkyl carbonate react is preferable.
- the number average molecular weight (Mn) of the aliphatic polycarbonate polyol (a1) or alicyclic polycarbonate polyol (a2) is preferably in the range of 500 to 3000, more preferably in the range of 1000 to 2000. If the Mn of (a1) and (a2) is within such a range, the desired radical-curable hot-melt urethane resin composition has the shape retention, coating workability, initial cohesive force, and aliphatic polyether described later. Excellent properties such as miscibility with other components such as polyol (a3) and alicyclic polyester polyol (a4) can be imparted.
- the number average molecular weight (Mn) described in the present invention is a value measured by the gel permeation chromatography method (GPC method) using polystyrene as a molecular weight standard under the following conditions.
- the number average molecular weight (Mn) described in the present invention is a value measured by the gel permeation chromatograph method (GPC method) in terms of polystyrene under the following conditions.
- Resin sample solution 0.4% tetrahydrofuran (THF) solution
- Measuring device model number HLC-8220GPC (manufactured by Tosoh Corporation)
- Eluent Tetrahydrofuran (THF)
- aliphatic polyether polyol (a3) for example, one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and the like are produced by addition polymerization of a compound having two or more active hydrogens.
- polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran for example, trade name: PTMG, manufactured by Mitsubishi Chemical Corporation
- polytetramethylene glycol derivatives obtained by copolymerization of tetrahydrofuran and alkyl-substituted tetrahydrofuran neopentyl
- examples thereof include polytetramethylene glycol derivatives obtained by copolymerization of glycol and tetrahydrofuran (for example, trade name: PTXG, manufactured by Asahi Kasei Fibers Co., Ltd.).
- polytetramethylene glycol PTMG
- polytetramethylene glycol derivative PTXG
- aliphatic polyether polyol (a3) a polyether polyol having an alicyclic structure may be used.
- Examples of the compound having two or more active hydrogens include water, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, Tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6- Hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecane Diol, 2-methyl-1,3-propanediol, neopentyl
- examples of the aliphatic polyester polyol that can be used in the polyol (A) include an aliphatic polyester polyol obtained by esterifying a low molecular weight polyol and a polycarboxylic acid, ⁇ -caprolactone, and ⁇ -valero. Polyester obtained by ring-opening polymerization reaction of a cyclic ester compound such as lactone, a copolymer polyester thereof, or the like can be used.
- low molecular weight polyol examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, and 1,2-butanediol.
- polycarboxylic acid examples include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid aliphatic polycarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexanetricarboxylic acid and the like.
- the alicyclic polycarboxylic acids and their anhydrides or ester derivatives can be used alone or in combination of two or more.
- an alicyclic polyester polyol an aliphatic polyester polyol obtained by ring-opening polymerization reaction of ⁇ -caprolactone, 1,4-butanediol and adipic acid Aliphatic polyester polyols obtained by esterification reaction are preferred.
- Mn of the aliphatic polyether polyol (a3) is preferably in the range of 500 to 3000, and more preferably in the range of 1000 to 3000.
- the properties such as mold retention, coating workability, initial cohesive force, and miscibility with other components such as (a1) and (a3) are excellent.
- polyol (A) other polyols can be used together with the aliphatic polycarbonate polyol (a1), the alicyclic polycarbonate polyol (a2), and the aliphatic polyether polyol (a3).
- Examples of the other polyols include polyester polyols and acrylic polyols.
- alicyclic polyester polyol (a4) which is one of polyester polyols is particularly preferable.
- the alicyclic polyester polyol (a4) is used in combination with the above (a1) to (a3) and used as a polyol (A) in a radical curable hot melt urethane resin composition, It is possible to obtain excellent properties such as hot-melt property that allows rapid cooling and solidification and high transparency (light transmittance) for efficiently guiding LED (light emitting diode) light and the like.
- the alicyclic polyester polyol (a4) is obtained by a condensation reaction of an aliphatic dicarboxylic acid and an alicyclic diol, or obtained by a condensation reaction of an alicyclic dicarboxylic acid and an aliphatic diol. Things. If the above (a4) is used in combination as a raw material for synthesizing the polyol (A), the compatibility of each polyol component can be further improved, and the initial cohesive strength of the resulting radical-curable hot melt urethane resin composition with respect to the substrate can be increased. This is more preferable because it can be further enhanced and flexibility and durability (particularly hydrolysis resistance) can be further improved. Among the above (a4), the use of a polyol having a cyclohexane ring is more preferable because the above effect can be further improved.
- the combination of the aliphatic dicarboxylic acid and the alicyclic diol used for the synthesis of the alicyclic polyester polyol (a4), or the combination of the alicyclic dicarboxylic acid and the aliphatic diol is compatible with each polyol component, or What is necessary is just to select suitably considering the target performance etc. of a radical curable hot-melt urethane resin composition.
- Examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, and the like.
- dicarboxylic acids having 6 or less carbon atoms are preferable, and succinic acid and adipic acid are more preferable.
- the alicyclic diol is not particularly limited, but 1,4-cyclohexanedimethanol (CHDM) and its derivatives are preferable because excellent transparency can be obtained.
- CHDM 1,4-cyclohexanedimethanol
- Examples of the alicyclic dicarboxylic acid include hexahydrophthalic acid and / or its isomer, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2- Examples thereof include cyclohexanedicarboxylic acid, and among these, hexahydrophthalic acid and / or an isomer thereof are preferable from the viewpoint of transparency.
- Examples of the aliphatic diol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, and 1,2-butanediol.
- various carboxylic acid derivatives such as lower alkyl esters, acid anhydrides, acid halides such as methyl ester compounds may be used.
- Mn of the alicyclic polyester polyol (a4) is preferably 500 to 5000, and more preferably 1000 to 3000. If the Mn of the above (a4) is within such a range, a radical curable hot melt capable of better forming a cured product such as an optical formed body having excellent initial cohesive force and appropriate flexibility according to the purpose. A urethane resin composition can be obtained.
- the radical curable hot melt urethane resin composition of the present invention in the polyol (A), the aliphatic polycarbonate polyol (a1), the alicyclic polycarbonate polyol (a2), or the aliphatic polyether polyol (a3). ), And the use of the alicyclic polyester polyol (a4) as a “compatibilizer”, a more uniform compatible system can be formed, resulting in higher flexibility and excellent mechanical strength. This is preferable.
- the content of the (a1) to (a4) is preferably 20 to 95 parts by mass of the (a1) or (a2), or 20 of the (a3), in 100 parts by mass of the total amount of the polyol (A).
- -95 parts by mass (a4) is 10-50 parts by mass, more preferably, (a1) or (a2) is 50-95 parts by mass, (a3) is 50-95 parts by mass, (A4) is 10 to 30 parts by mass. If the above (a4) is contained in such a range, the compatibility can be further improved, and the good initial cohesive force, adhesiveness and transparency to the base material of the radical curable hot melt urethane resin composition can be maintained more stably. It is more preferable because it can further improve moderate flexibility and excellent durability (particularly hydrolysis resistance).
- the hot melt urethane resin composition for the purpose of improving durability (hydrolysis resistance) and strength retention, for example, trifunctional or higher polyhydric alcohols such as trimethylolpropane and polypropylene glycol are synthesized with polyol.
- the hot melt urethane resin composition obtained by such a method has a problem that it is inferior in thermal stability. Therefore, in the radical curable hot melt urethane resin composition of the present invention, excellent thermal stability can be obtained by using a specific polyol (A) without using a trifunctional or higher polyhydric alcohol as described above. Can also be secured.
- the alicyclic polyisocyanate (B) may be any polyisocyanate having an aliphatic cyclic structure, such as isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, 2,4- and / or 2,6-methylcyclohexane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- And / or 2,6-norbornane diisocyanate, dimer acid diisocyanate, bicycloheptane triisocyanate, and the like may be used alone or in combination of two or more.
- isophorone diisocyanate 1,3-bis (isocyanatomethyl) cyclohexane,
- HMDI 4,4′-dicyclohexylmethane diisocyanate
- IPDI isophorone diisocyanate
- BICH 1,3-bis (isocyanatomethyl) cyclohexane
- the polyol (A) and the alicyclic polyisocyanate (B) are reacted to form an isocyanate group-terminated hot melt urethane prepolymer (C) (hereinafter referred to as “urethane prepolymer having an isocyanate group at the molecular end”).
- the synthesis method is not particularly limited, and a known method can be adopted.
- polyol (A) with which reaction container was charged ie, aliphatic polycarbonate polyol (a1), alicyclic polycarbonate polyol (a2), or fat
- a polyol mixture containing an aliphatic polyether polyol (a3) and, if necessary, an alicyclic polyester polyol (a4) is heated under normal pressure or reduced pressure to remove moisture in advance, and then required for the polyol mixture
- the isocyanate group content (%) is substantially constant after charging and mixing the amount of the alicyclic polyisocyanate (B) by an appropriate method such as dropping, splitting, batch, continuous, etc.
- the production of the urethane prepolymer (C) is usually carried out without a solvent, but may be carried out in an organic solvent.
- organic solvent When reacting in an organic solvent, it is necessary to select an organic solvent that does not impair normal reaction and good quality.
- the organic solvent include ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone; and ether esters such as methyl cellosolve acetate and butyl cellosolve acetate.
- Solvent aromatic hydrocarbon solvents such as toluene and xylene, and amide solvents such as dimethylformamide and dimethylacetamide. These may be used alone or in combination of two or more.
- the amount of the organic solvent used is not particularly limited as long as it does not inhibit the reaction. However, the organic solvent used in the reaction is removed by an appropriate method such as heating under reduced pressure or drying at normal pressure during or after the reaction.
- the melt viscosity of the urethane prepolymer (C) is preferably 500 mPa ⁇ s or more (measurement temperature: 100 ° C., when the resin composition is used as an optical molded body such as a light guide plate or a light guide fiber).
- the measurement temperature is abbreviated below.
- a film-like optical molded body such as a protective film, a key sheet film, an optical film, a light guide film, and a light guide sheet
- the range is s, more preferably 500 to 4300 mPa ⁇ s. If the melt viscosity of the urethane prepolymer (C) is within such a range, the target resin composition is used, and no repelling occurs during molding of a film or sheet, and excellent flatness can be obtained.
- melt viscosity as used in the field of this invention is the value measured with the cone-plate viscometer (made by ICI company) at the measurement temperature of 100 degreeC unless there is particular notice.
- the equivalent weight of the isocyanate group of the urethane prepolymer (C) is not particularly limited when used as an optical molded body such as a light guide plate or a light guide fiber, but for example, a protective film, a key sheet film, an optical When used as a film-like optical molded article such as a film, a light guide film, or a light guide sheet, the thickness is preferably in the range of 500 to 3000, more preferably in the range of 500 to 2000.
- the equivalent weight of the isocyanate group of the urethane prepolymer (C) is within such a range, when used as a film or sheet, excellent transparency and appropriate flexibility can be obtained, and coating onto a substrate is possible. Occasionally no repelling occurs and surface smoothness is excellent.
- the equivalent weight of the isocyanate group as referred to in the present invention means the total weight of the polyol (A) and the alicyclic polyisocyanate (B) from the equivalent derived from the alicyclic polyisocyanate (B). The value obtained by dividing the equivalent of (A) by the value.
- Examples of methods for obtaining the urethane prepolymer (C) by reacting the polyol (A) and the alicyclic polyisocyanate (B) in the absence of a solvent include the following production methods.
- the isocyanate group of the alicyclic polyisocyanate (B) and the polyol is preferably in the range of 1.1 to 20.0, more preferably in the range of 1.1 to 13.0. More preferably, it is in the range of 1.1 to 5.0, and particularly preferably in the range of 1.5 to 3.0.
- [NCO / OH equivalent ratio] is in such a range, a radical curable hot melt urethane resin composition having a melt viscosity suitable for application to a substrate and excellent shape retention by cooling and solidification is obtained. Can do.
- Reaction conditions for producing the urethane prepolymer (C) may be appropriately set in consideration of various conditions such as safety, quality, cost and the like, and are not particularly limited. Preferably, it is in the range of 70 to 120 ° C., and the reaction time is preferably in the range of 30 minutes to 5 hours.
- the softening temperature of the urethane prepolymer (C) is preferably in the range of 30 to 120 ° C, more preferably in the range of 40 to 100 ° C. If the softening temperature of (C) is within such a range, the solidification time after coating is fast, the initial cohesive force is easily developed, and the initial adhesiveness is excellent, which is preferable.
- the softening temperature as used in the field of this invention is the value measured based on Japanese Industrial Standard (henceforth JIS) K 2207.
- a method for adjusting the softening temperature of the urethane prepolymer (C) to an appropriate temperature range for example, (1) adjustment by molecular weight of the urethane prepolymer (adjustment of the molar ratio of polyol and polyisocyanate, (Use of high molecular weight polyol, use of high molecular weight polymer, etc.), (2) Adjustment by crystallinity of ethylene chain of polyester polyol, (3) Adjustment by molecular structure of polyol or polyisocyanate, (4) Adjustment by urethane bond, etc.
- adjustment by molecular weight of the urethane prepolymer adjustment of the molar ratio of polyol and polyisocyanate, (Use of high molecular weight polyol, use of high molecular weight polymer, etc.
- Adjustment by crystallinity of ethylene chain of polyester polyol (3) Adjustment by molecular structure of polyol or polyisocyanate, (4) Adjustment by
- a tertiary amine catalyst or an organometallic catalyst can be used as the catalyst, if necessary, and is not particularly limited.
- the isocyanate group of the urethane prepolymer (C) is converted into a (meth) acryloyl group by a (meth) acrylate compound (D) having an active hydrogen-containing group (hereinafter also referred to as (meth) acrylate compound (D)).
- the introduced hot melt urethane (X) is mixed with the radical polymerization initiator (Y) together with the hot melt urethane (X) to obtain the radical curable hot melt urethane resin composition of the present invention.
- the hot melt urethane (X) into which the (meth) acryloyl group is introduced is obtained.
- the “active hydrogen-containing group” means a functional group reactive with an isocyanate group, for example, a group having active hydrogen such as a hydroxyl group, an amino group, a carboxyl group, or a mercapto group.
- a hydroxyl group or an amino group Preferably a hydroxyl group or an amino group, more preferably a hydroxyl group.
- the (meth) acrylate compound (D) having an active hydrogen-containing group include (hydroxy) (meth) acrylate compounds having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, butanediol mono (meth) acrylate, 2-hydroxyethyl Examples thereof include caprolactone-modified products of (meth) acrylate and glycidol di (meth) acrylate.
- hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)
- Examples of the (meth) acrylate compound having an amino group include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
- excellent curability by irradiation with active energy rays such as infrared rays, visible rays, ultraviolet rays, X-rays, electron rays, ⁇ rays, ⁇ rays, ⁇ rays, sunlight, etc., and particularly improved mechanical strength.
- 2-hydroxyethyl acrylate (HEA) is preferable because it is effective for the above. These may be used alone or in combination of two or more.
- (meth) acrylate refers to one or both of methacrylate and acrylate
- (meth) acryloyl group refers to one or both of methacryloyl group and acryloyl group
- “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid.
- the amount of the (meth) acrylate compound (D) used is preferably in the range of 5.0 to 20.0 parts by mass, more preferably 5.0 to 100 parts by mass of the urethane prepolymer (C). It is in the range of ⁇ 15.0 parts by mass.
- a urethanization catalyst can be used as necessary.
- the urethanization catalyst can be appropriately added at any stage of the urethanization reaction.
- the urethanization reaction is preferably performed until the isocyanate group content (%) becomes substantially constant.
- the urethanization catalyst is not particularly limited, and a conventionally known catalyst can be used.
- nitrogen-containing compounds such as triethylamine, triethylenediamine, N-methylmorpholine, potassium acetate, zinc stearate, octyl acid
- An organometallic salt such as monotin or an organometallic compound such as dibutyltin dilaurate can be used.
- the amount of the urethanization catalyst used is not particularly limited as long as it does not adversely affect the safety during the reaction, the stability of the intermediate or product, the quality, etc.
- the melt viscosity of the hot melt urethane (X) into which the (meth) acryloyl group is introduced is preferably 500 mPa ⁇ when the resin composition is used as an optical molded body such as a light guide plate or a light guide fiber. s or more (measurement temperature: 100 ° C., hereinafter abbreviated measurement temperature), for example, when used as a film-like optical molded body such as a protective film, a key sheet film, an optical film, a light guide film, and a light guide sheet. Is preferably in the range of 500 to 5000 mPa ⁇ s, more preferably in the range of 500 to 4300 mPa ⁇ s. If the melt viscosity of the hot-melt urethane (X) is within such a range, the target resin composition is used, and no repelling occurs at the time of forming a film or sheet, and excellent planar smoothness can be obtained.
- the radical curable hot melt urethane resin composition of the present invention comprises a radical curing reaction by irradiation of active energy rays of an isocyanate group and a double bond of a hot melt urethane (X) into which (meth) acryloyl group is introduced, and an isocyanate group.
- Moisture (water) curing reaction occurs together, resulting in mold retention, flexibility, mechanical strength, durability (particularly hydrolysis resistance) after application to the substrate, adhesion to the substrate, and rapid curing. Excellent performance, such as properties, can be exhibited.
- the radical curable hot melt urethane resin composition of the present invention can be obtained by blending and mixing a predetermined amount of radical polymerization initiator (Y) together with the hot melt urethane (X).
- the radical polymerization initiator (Y) acts to initiate a curing reaction by reacting itself or a decomposition product thereof with an active site of a reactive oligomer or (meth) acrylate monomer by the action of light, heat or a catalyst. It is what has.
- the amount of the radical polymerization initiator (Y) is preferably in the range of 0.5 to 5.0 parts by mass, more preferably 1.0 to 100 parts by mass with respect to 100 parts by mass of the urethane prepolymer (C).
- the range is 3.0 parts by mass. If the blending amount of the radical polymerization initiator (Y) is within such a range, the curability of the resin composition can be appropriately adjusted according to the processing conditions. As a result, the adhesion and the shape retention after application to the substrate can be adjusted. A radically curable hot melt urethane resin composition having excellent properties can be obtained.
- the curing time becomes too long and the processability is inferior, and when it exceeds 5.0 parts by mass, the curing reaction May occur too quickly, and in any case, there is a risk of malfunction.
- the (meth) acrylate compound (D) is reacted in a range of more than 50 mol% of the total number of terminal NCO groups of the urethane prepolymer (C) and not more than 100 mol%. It is preferable to add after making it.
- Reaction conditions may be appropriately set in consideration of various conditions such as safety, quality, and cost, and are not particularly limited.
- the reaction temperature is preferably in the range of 80 to 120 ° C.
- the mixing time is preferably in the range of 30 minutes to 2 hours.
- radical polymerization initiator (Y) known ones can be used, and examples thereof include a photopolymerization initiator and a peroxide, and a photopolymerization initiator is preferable from the viewpoint of productivity.
- photopolymerization initiator conventionally known ones such as alkylphenone photopolymerization initiators such as benzophenone, camphorquinone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators can be used. There are no particular restrictions.
- photopolymerization initiators include, for example, benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t -Thioxanthones such as butylanthraquinone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON (for example, Darocur 1173 manufactured by Ciba Specialty Chemicals Co., Ltd.), benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone (for example, Ciba Specialty Chemicals Co., Ltd.) Irgacure 184
- photopolymerization initiators such as Irgacure 184 and Irgacure 651 that can impart excellent curability by irradiation with active energy rays such as ultraviolet rays are preferable.
- peroxide examples include conventionally known peroxides such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, cumene hydroperoxide, and peroxyester. Can be used. These may be used alone or in combination of two or more. Among these, peroxyesters and peroxydicarbonates are preferable for curing under high temperature conditions of 80 to 120 ° C., and peroxydicarbonate is particularly preferable. Examples of the peroxydicarbonate include di (4-t-butylcyclohexyl) peroxydicarbonate, and commercially available products include peroyl TCP (manufactured by NOF Corporation). Among these, peroyl TCP which can impart excellent curability by irradiation with active energy rays such as ultraviolet rays is preferable.
- a known photosensitizer can be added to the radical curable hot melt urethane resin composition of the present invention as required.
- the photosensitizer include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethyl. Examples include aminoacetophenone. These photosensitizers may be used alone or in combination of two or more.
- a known polyfunctional (meth) acrylate compound can also be blended with the radical curable hot melt urethane resin composition of the present invention.
- the polyfunctional (meth) acrylate compound can contribute to the formation of a crosslinked structure by a double bond in the molecule, the curing speed of the hot melt urethane resin composition and the crosslinking density after curing are further improved. Thus, good durability and fluff resistance can be imparted by the obtained film or sheet.
- polyfunctional means having two or more polymerizable double bonds in the molecule, and preferably having 2 to 4 polymerizable double bonds.
- the compounding amount of the polyfunctional (meth) acrylate compound is preferably in the range of 5 to 30 parts by mass, more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the radical curable hot melt urethane resin composition. Range. If the blending amount of the polyfunctional (meth) acrylate compound is within such a range, the adjustment to the target melt viscosity can be facilitated, and the durability and fluff resistance are further improved.
- polyfunctional (meth) acrylate compound examples include polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate.
- an alkylene oxide, an aliphatic ester, caprolactone or the like added to the polyfunctional (meth) acrylate compound can be used.
- the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.
- polyfunctional (meth) acrylate compound since it can obtain the outstanding sclerosis
- additives include, for example, foam stabilizers, antioxidants, defoamers, ultraviolet absorbers, abrasive grains, antioxidants, antifoaming agents, leveling agents, polymerization inhibitors, wetting agents (thickening agents). ), Thixotropic agent, filler, pigment, dye, colorant, thickener, surfactant, flame retardant, plasticizer, lubricant, antistatic agent, heat stabilizer, tackifier, curing catalyst, stabilizer, Illustrative examples include fluorescent brighteners, silane coupling agents, and waxes. Further, as necessary, a known thermoplastic resin, thermosetting resin, or the like can be appropriately selected and used as a blending resin as long as the object of the present invention is not impaired. In addition, the said additive is only an example, As long as the objective of this invention is not inhibited, the kind and usage-amount are not specifically limited. These additives may be added at any stage of production.
- tackifier examples include rosin resins, rosin ester resins, hydrogenated rosin ester resins, terpene resins, terpene phenol resins, hydrogenated terpene resins, and C 5 aliphatics as petroleum resins. Resins, C 9 aromatic resins, C 5 and C 9 copolymer resins, and the like can be used.
- plasticizer examples include dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trioctyl phosphate, epoxy plasticizer, toluene-sulfoamide, chloroparaffin, adipine Acid esters, castor oil, and the like can be used. Examples include methyl acid phosphate (AP-1) and acrylic surface conditioner (BYK-361N).
- hindered phenol compounds for example, hindered phenol compounds, benzotriazole compounds, hindered amine compounds and the like can be used.
- filler for example, silicic acid derivatives, talc, metal powder, calcium carbonate, clay, carbon black and the like can be used.
- ultraviolet absorber examples include benzotriazole compounds represented by methylhydroxyphenylbenzotriazole, butylmethylhydroxyphenylbenzotriazole, dibutylhydroxyphenylbenzotriazole, bis (tetramethylpiperidyl) sebacate, bis (pentamethyl), and the like. And hindered amine compounds such as piperidyl) sebacate.
- the “active energy rays” used when the cured film is produced by curing the coating film of the radical curable hot melt resin composition of the present invention for example, sunlight, infrared rays, visible rays, ultraviolet rays, X-rays, Electron beams, ⁇ rays, ⁇ rays, ⁇ rays, sunlight, and the like can be used, but from the viewpoint of the cost and productivity of the device, preferably infrared rays, visible rays, ultraviolet rays, electron beams, sunlight, More preferably, it is ultraviolet rays.
- the light source examples include an electron beam irradiation device, a mercury lamp (ultra high pressure, high pressure, medium pressure, low pressure), a metal halide lamp, a tungsten lamp, an Ar laser, a He—Cd laser, a solid laser, a xenon lamp, a high frequency induction mercury lamp, Various lamps such as a hydrogen lamp, a deuterium lamp, a halogen lamp, a carbon arc lamp, a fluorescent lamp, and sunlight can be used and are not particularly limited.
- the irradiation intensity of the active energy ray varies depending on the type of the active energy ray to be used, and is not particularly limited.
- the irradiation intensity is preferably 1 to 20 Mrad.
- the irradiation intensity is preferably 50 to 1500 mJ / cm 2 .
- the resin composition is applied to the surface of a release substrate, for example, a slit coater such as a curtain flow coater method or a die coater method.
- a slit coater such as a curtain flow coater method or a die coater method.
- a method of coating by an appropriate method such as a coating method, a knife coater method, a roll coater method, etc., a method of heating and curing after drying as required, or an injection breath molding method of compressing a resin in a mold.
- the conditions for curing after coating differ depending on the type of radical polymerization initiator (Y) used, it may be set as appropriate and is not particularly limited.
- a photoinitiator as said photoinitiator (Y)
- active energy rays such as an ultraviolet-ray
- it is preferably heat-cured at 80 to 250 ° C. for about 1 to 60 minutes.
- heat curing may be performed at 40 to 200 ° C. for about 1 to 10 hours.
- An optical molded body using the radical-curable hot-melt urethane resin composition of the present invention has flexibility, durability (particularly hydrolysis resistance), transparency (light transmittance), thermal stability, yellowing resistance. (Non-yellowing), excellent properties such as adhesion to substrates, productivity (fast curing), etc., for example, light guide film, light guide sheet, protective film, key sheet film, optical It can be suitably used for various light guide articles such as films, light guide plates, and light guide fibers.
- the film thickness is preferably in the range of 5 ⁇ m to 1000 ⁇ m.
- the film thickness is within this range, moderate flexibility, excellent durability (especially hydrolysis resistance), transparency (light transmittance), thermal stability, yellowing resistance (no yellowing), substrate It is possible to obtain properties such as adhesion to the substrate and productivity (fast curability).
- a film having a thickness of 200 ⁇ m or less is defined as “film”, and a film having a thickness exceeding 200 ⁇ m is defined as “sheet”.
- the polyol (A) contains the aliphatic polycarbonate polyol (a1), the alicyclic polycarbonate polyol (a2), or the aliphatic polyether polyol (a3) (particularly PTMG or PTMG derivative). Appropriate flexibility, excellent durability (particularly hydrolysis resistance), and transparency (light transmittance) can be imparted.
- the polyol (A) contains the alicyclic polyester polyol (a4) as a “compatibilizer” together with the above (a1), (a2), or (a3).
- Compatibility can be further improved, good initial cohesion with the substrate can be maintained, moderate flexibility and excellent durability (especially hydrolysis resistance) can be further improved, and the coating is heated and melted. Accelerates solidification by cooling after coating, and can achieve both hot melt properties and transparency.
- Characteristic [3] By using especially alicyclic polyisocyanate (B) as polyisocyanate, the isocyanate group of said alicyclic polyisocyanate (B) and said polyol (A) and moisture (water) are favorable. Able to provide performance such as reactivity, excellent heat resistance, yellowing resistance and transparency (light transmittance).
- the radical-curable hot-melt urethane resin composition of the present invention has “hot-melt property” that can be quickly cooled and solidified after being applied to a base material, such as infrared rays, visible rays, ultraviolet rays, X-rays, and electron beams. , ⁇ -rays, ⁇ -rays, ⁇ -rays, solar energy and other active energy ray irradiations, and also has “fast curing” properties, moderate flexibility and excellent durability (especially hydrolysis resistance) ), High transparency (light transmittance) for efficiently guiding LED (light emitting diode) light, thermal stability that does not cause deterioration, deformation, discoloration, etc.
- a base material such as infrared rays, visible rays, ultraviolet rays, X-rays, and electron beams.
- ⁇ -rays, ⁇ -rays, ⁇ -rays, solar energy and other active energy ray irradiations and also has “fast curing”
- Thickening rate (melt viscosity V 12 after 12 hours at 100 ° C.) / (Initial melt viscosity V 0 ) Evaluation criteria for thermal stability. ⁇ : When the viscosity increase rate is 1.00 or more and less than 1.20, the thermal stability is excellent. X: When the viscosity increase rate is 1.20 or more, the thermal stability is poor.
- UV irradiation by passing through the inside once at a strength of 120 W / cm and a conveyor speed of 5 m / min), and then left in a constant temperature and humidity chamber at a temperature of 23 ° C. and a relative humidity of 65% for 3 days to perform a moisture curing reaction. Proceeded. The film formed after standing was peeled from the release paper to obtain a cured film.
- the above-mentioned ultraviolet irradiation amount is a value measured in a wavelength range of 400 nm and 900 nm using a UV checker UVR-N1 (manufactured by Nippon Battery Co., Ltd.).
- the total light transmittance (%) of the cured film prepared above was measured using a haze meter (Nippon Denshoku Industries Co., Ltd., model: NDH-2000) in accordance with JIS K7361-1.
- transparency of the cured film was evaluated according to the following reference
- the aliphatic polycarbonate polyol (a1) is cooled to 70 ° C., and 24.0 parts by mass of dicyclohexylmethane-4,4′-diisocyanate (abbreviated as HMDI) is added as the alicyclic polyisocyanate (B).
- HMDI dicyclohexylmethane-4,4′-diisocyanate
- the temperature was raised to 100 ° C. and the reaction was continued for 3 hours until the isocyanate group content became constant, to obtain an isocyanate group-terminated hot-melt urethane prepolymer (C-1).
- the urethane prepolymer (C-1) had a melt viscosity at 100 ° C. of 3600 mPa ⁇ s and an isocyanate group content (NCO%) of 3.89% by mass.
- the properties of the urethane prepolymer (C-1) obtained in Synthesis Example 1 are summarized in Table 1.
- the composition and properties of the hot melt urethane (X-1) are summarized in Table 1.
- the melt viscosity at 100 ° C. of the hot melt urethane (X-1) was 3690 mPa ⁇ s, and the isocyanate group content (NCO%) was 1.75% by mass.
- the ratio of the number of NCO groups reacted with the (meth) acrylate compound (D) having an active hydrogen-containing group to the total number of isocyanate groups of the urethane prepolymer (C-1) [[OH / NCO] ⁇ 100 (%)] according to a conventional method, adding an excess of dibutylamine, reacting an isocyanate group with dibutylamine, and then determining the amount of dibutylamine remaining by the back titration method using hydrochloric acid. Can be calculated and determined.
- the urethane prepolymers (C-2) to (C-17) in Tables 1 and 2 were also treated in the same manner as in the above (C-1) with respect to the (meth) acrylate compound (D).
- ⁇ Optical molded article 1 using radical curable hot melt urethane resin composition The radical curable hot-melt urethane resin composition (RHM1) obtained above was melted by heating to 100 ° C., and 100 ⁇ m on the 70 ⁇ m-thick mold release treated PET as the base material using a knife coater heated to 100 ° C. It was applied with a thickness of.
- a conveyor type ultraviolet irradiation device CSOT-40 (made by Nippon Battery Co., Ltd., using a high-pressure mercury lamp) is set so that the amount of ultraviolet irradiation is 145 mJ / cm 2 every time the inside of the device is passed through the coating surface.
- UV irradiation (UV irradiation) was carried out by passing once through the inside of 120 W / cm in strength and 5 m / min conveyor speed.
- the optical molded article 1 after moisture curing was obtained by leaving it in a constant temperature and humidity chamber having a temperature of 23 ° C. and a relative humidity of 65% for 3 days.
- Table 1 shows the property evaluation results of the optical molded article 1 using the radical curable hot melt urethane resin composition (RHM1) of the present invention.
- the optical molded article 1 disappeared after UV irradiation, and had excellent performance such as moderate flexibility, mechanical strength, durability (hydrolysis resistance), and yellowing resistance. .
- Example 2 the amount of HEA used as the (meth) acrylate compound (D) having an active hydrogen-containing group was 5.9 parts by mass (Example 2) and 8.1 parts by mass (Example 3), respectively.
- the radical curable hot melt urethane resin composition (RHM2 and RMM3) of the present invention was obtained in the same manner as in Example 1 except that the above was changed.
- the ratio of the number of NCO groups reacted with HEA as the (meth) acrylate compound (D) to the total number of isocyanate groups of the urethane prepolymer (C-1) [[OH / NCO] ⁇ 100 (%) ] was set such that the theoretical value of the total number of NCO groups was 75% (Example 2) and 100% (Example 3). Then, by the same operation as in Example 1, cured optical molded products 2 and 3 were obtained using the radical curable hot melt urethane resin composition (RHM2 and RHM3) of the present invention. The evaluation results of the optical molded products 2 and 3 are shown in Table 1. The optical molded products 2 and 3 lost surface tack after UV irradiation, and had excellent performance such as moderate flexibility, mechanical strength, durability (hydrolysis resistance), and yellowing resistance. .
- the radical curable hot-melt urethane resin composition (RHM29 to 32) is heated and melted to 100 ° C., and is applied onto a 70 ⁇ m-thick mold release-treated PET as a substrate using a knife coater heated to 100 ° C. It apply
- the coated surface was left for 10 minutes in a drier heated to 150 ° C. to be cured by heating. Next, it was left in a constant temperature and humidity chamber at a temperature of 23 ° C. and a relative humidity of 65% for 3 days to obtain moisture-cured optical molded articles 29 to 32.
- Table 1 shows the characteristic evaluation results of optical molded articles 29 to 32 using the radical curable hot melt urethane resin composition (RHM 29 to 32) of the present invention.
- the optical molded articles 29 to 32 have surface tack disappeared after heat curing, and have excellent performance such as moderate flexibility, mechanical strength, durability (hydrolysis resistance), and yellowing resistance. It was.
- CHDM cyclohexanedimethanol
- SUCA succinic acid
- HHPA hexahydrophthalic anhydride
- UC-100 An alicyclic polycarbonate polyol of Mn 1000 obtained by reacting cyclohesanedimethanol and dialkyl carbonate, manufactured by Ube Industries, Ltd.
- Irgacure 651 trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.
- photopolymerization initiator Irgacure 184 trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.
- photopolymerization initiator Parroyl TCP trade name, manufactured by NOF Corporation Peroxydicarbonate peroxide
- the radical curable hot-melt urethane resin composition of the present invention is in a hot-melt state at the time of application, but has a hot-melt property that quickly cools and solidifies after application to a substrate, and, for example, infrared, visible light, ultraviolet, X-ray, It has two characteristics of fast curing by irradiation with active energy rays such as electron beam, ⁇ ray, ⁇ ray, ⁇ ray, sunlight, etc., moderate flexibility and durability (especially hydrolysis resistance), Excellent in transparency (light transmittance), heat stability, yellowing resistance (non-yellowing), adhesion to substrates, and productivity (fast curing).
- active energy rays such as electron beam, ⁇ ray, ⁇ ray, ⁇ ray, sunlight, etc.
- optical molded body for example, optical molded body (light guide film) , Light guide sheet, protective film, key sheet film, optical film, light guide plate, light guide article such as light guide fiber), etc., and useful for a wide range of applications such as adhesives, adhesives, coating agents, adhesives It is.
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Abstract
Description
本発明のラジカル硬化性ホットメルトウレタン樹脂組成物は、(メタ)アクリロイル基を有するホットメルトウレタン(X)(以下、ホットメルトウレタン(X)という。)とラジカル重合開始剤(Y)とを所定の範囲内の量で含有する。
本発明では、ポリオール(A)として、耐黄色性や透明性を向上できることから、芳香族環式構造を有さないポリオールを用いる。かかるポリオール(A)としては、好ましくは脂肪族ポリカーボネートポリオール、脂環式ポリカーボネートポリオール、脂肪族ポリエーテルポリオール、脂環式ポリエステルポリオール、及び脂肪族ポリエステルポリオールなどが挙げられ、より好ましくは脂肪族ポリカーボネートポリオール、脂環式ポリカーボネートポリオール、脂肪族ポリエーテルポリオール、脂環式ポリエステルポリオールが挙げられる。
本発明に記載の数平均分子量(Mn)の測定は、ポリスチレン換算によるゲル・パーミエイション・クロマトグラフ法(GPC法)により、下記条件にて測定した値である。
樹脂試料溶液;0.4%テトラヒドロフラン(THF)溶液
測定装置型番;HLC-8220GPC(東ソー株式会社製)
カラム ;TSKgel(東ソー株式会社製)
溶離液 ;テトラヒドロフラン(THF)
実施例及び比較例で得た夫々のウレタンプレポリマー(C)及びホットメルトウレタン(X)の溶融粘度(mPa・s)をコーンプレート粘度計(ICI社製)にて測定温度100℃で測定した。以下、単位及び測定温度は省略する。
実施例及び比較例で得た夫々のウレタンプレポリマー(C)の軟化温度(乾球式軟化点)(℃)をJIS K 2207に準拠して、昇温速度5℃/分の条件にて測定した。
実施例及び比較例で得た夫々のラジカル硬化性ホットメルトウレタン樹脂組成物(溶融粘度V0、単位:mPa・s、測定温度100℃)を300ml金属缶に300g秤量して、窒素置換後に密閉し、内温100℃の乾燥機中に12時間放置後の前記樹脂組成物の溶融粘度V12(単位:mPa・s、測定温度100℃)を測定した。
次いで、下式より算出した溶融粘度の増粘率から、下記の基準に従い熱安定性を評価した。
増粘率=(100℃で12時間後の溶融粘度V12)/(初期の溶融粘度V0)
熱安定性の評価基準。
○:増粘率が1.00以上1.20未満の場合、熱安定性に優れる。
×:増粘率が1.20以上の場合、熱安定性に劣る。
実施例及び比較例で得た夫々のラジカル硬化性ホットメルトウレタン樹脂組成物を100℃で加熱溶融させて、100℃に加熱されたナイフコーターを用いて、基材である70μm厚みの離型処理PET上に100μmの厚みにて塗布した。次いで、前記塗布面に、装置内を1回通過させるごとに145mJ/cm2の紫外線照射量となるように設定したコンベアタイプの紫外線照射装置CSOT―40(日本電池株式会社製、高圧水銀ランプ使用、強度120W/cm、コンベアスピード5m/分)内を1回通過させることによって紫外線照射を行い、次いで、温度23℃、相対湿度65%の恒温恒湿槽中で3日間放置し湿気硬化反応を進行させた。放置後に形成されたフィルムを離型紙上から剥離し、硬化フィルムを得た。尚、上記の紫外線照射量は、UVチェッカーUVR-N1(日本電池株式会社製)を用いて、400nmと900nmの波長域において測定した値である。
上記で作成した硬化フィルムの全光線透過率(%)を、ヘーズメーター(日本電色工業株式会社製、機種:NDH-2000)を使用し、JIS K7361-1に準拠して測定した。尚、前記全光線透過率(%)の測定結果を基に、下記の基準に従い、硬化フィルムの透明性を評価した。
透明性の評価基準。
○:全光線透過率が90%以上の場合、透明性に優れる。
×:全光線透過率が90%未満の場合、透明性に劣る。
上記で作成した硬化フィルムを幅5mm×長さ70mmにカットして得た試験片を用いて、JIS K-7311に準拠してテンシロン(株式会社島津製作所製、ヘッドスピード=300mm/分)により引張特性を測定し、柔軟性を評価した。
尚、硬化フィルムの柔軟性は、引張特性のうちの100%モジュラスの値を基に、下記の基準に従い評価した。
柔軟性の評価基準
○:5.0MPa以下の場合、柔軟性に優れる。
△:5.0を超え10.0Mpa以下の場合、柔軟性は標準的。
×:10.0Mpaを超える場合、柔軟性に劣る。
上記で作成した硬化フィルムを、耐加水分解試験(促進試験条件:温度70℃、相対湿度95%、10週間保持)に供した後、上記の柔軟性の評価方法と同様の測定条件で引張特性を測定して、下記の基準に従い評価した。
耐加水分解性の評価基準。
○:強度保持率が90%以上の場合、耐加水分解性に優れる。
×:強度保持率が90%未満の場合、耐加水分解性に劣る。
上記で作成した硬化フィルムを、サンシャインウェザーメーター(スガ試験機株式会社製、測定温度83℃、雨なし、光源カーボンアーク)にて400時間暴露して、暴露前後の黄色度(イエローインデックス:Y.I)を多光源分光測色計(スガ試験機株式会社製)により測定し、その変化量(ΔY.I)を求めた。
尚、硬化フィルムの耐黄色性は、前記変化量(ΔY.I)を基に、下記の基準に従い評価した。
耐黄変性の評価基準。
○:黄色度の変化量(ΔY.I)が2以下の場合、耐変色性に優れる。
×:黄色度の変化量(ΔY.I)が2を超える場合、耐変色性に劣る。
上記で作製したUV照射及び熱硬化直後の硬化フィルムの表面タックの有無を、指触にて観察し、速硬化性を以下の基準に従い評価した。
速硬化性の評価基準。
○:全く表面タックが残っていない場合、速硬化性に優れる。
△:表面にごく微量なタックが残っている場合、速硬化性が標準的。
×:表面タックが明らかに残っている場合、速硬化性に劣る。
≪イソシアネート基末端ホットメルトウレタンプレポリマー(C-1)の合成≫
反応容器に、1,5-ペンタンジオール(1,5PDと略称。)と1,6-ヘキサンジオール(1,6HDと略称。)及びジアルキルカーボネートを反応させて得られる数平均分子量(Mn)2000の脂肪族ポリカーボネートポリオール(a1)(商標:DURANOL T-5652、旭化成ケミカルズ株式会社製)を80質量部加え、減圧条件下にて100℃に加熱して、水分率が0.05質量%になるまで脱水した。
次いで、前記脂肪族ポリカーボネートポリオール(a1)を70℃まで冷却し、脂環式ポリイソシアネート(B)としてジシクロヘキシルメタン-4,4’-ジイソシアネート(HMDIと略称。)を24.0質量部加えて、100℃まで昇温して、イソシアネート基含有量が一定となるまで3時間反応させ、イソシアネート基末端ホットメルトウレタンプレポリマー(C-1)を得た。
上記ウレタンプレポリマー(C-1)の100℃における溶融粘度は3600mPa・sであり、イソシアネート基含有量(NCO%)は3.89質量%であった。合成例1で得たウレタンプレポリマー(C-1)の性状を第1表にまとめた。
≪ウレタンプレポリマー(C-2)~(C-17)の合成≫
第1表及び第2表に記載の配合に従い、合成例1と同様の反応操作にて、ウレタンプレポリマー(C-2)~(C-17)を合成した。前記ウレタンプレポリマーの性状を第1表及び第2表にまとめた。
≪ラジカル硬化性ホットメルトウレタン樹脂組成物(RHM1)の製造≫
合成例1で得た前記イソシアネート基末端ホットメルトウレタンプレポリマー(C-1)100質量部を100℃で加熱溶融させ、活性水素含有基を有する(メタ)アクリレート化合物(D)として2-ヒドロキシエチルアクリレート(HEA)10.7質量部とオクチル酸第一錫0.01質量部を加えて、内温100℃にてNCO%が一定となるまで反応させ、(メタ)アクリロイル基を導入させたホットメルトウレタン(X)を得た。
前記ウレタンプレポリマー(C-1)の有するイソシアネート基総数に対して、活性水素含有基を有する(メタ)アクリレート化合物(D)としてHEAが反応したNCO基の数の割合〔[OH/NCO]×100(%)〕は、NCO基総数の理論値が55%になるように仕込んだ。
前記ホットメルトウレタン(X-1)の組成及び性状を第1表にまとめた。前記ホットメルトウレタン(X-1)の100℃における溶融粘度は3690mPa・sであり、イソシアネート基含有量(NCO%)は1.75質量%であった。
次いで、前記ホットメルトウレタン(X-1)を100質量部と、ラジカル重合開始剤(Y-1)であるイルガキュア 184(チバ・スペシャルティ・ケミカルズ株式会社製)2.0質量部を混合攪拌することにより、本発明のラジカル硬化性ホットメルトウレタン樹脂組成物(RHM1)を得た。
なお、前記ウレタンプレポリマー(C-1)の有するイソシアネート基総数に対して、活性水素含有基を有する(メタ)アクリレート化合物(D)が反応したNCO基の数の割合〔[OH/NCO]×100(%)〕は、定法に従い、過剰のジブチルアミンを添加し、イソシアネート基とジブチルアミンとを反応させ、次いで残存するジブチルアミンの量を、塩酸を用いた逆滴定法により、イソシアネート基量を算出し求めることができる。
尚、前記(C-1)と同様の方法にて、第1表及び第2表中のウレタンプレポリマー(C-2)~(C-17)についても、前記(メタ)アクリレート化合物(D)が反応したNCO基の数の割合〔[OH/NCO]×100(%)〕を求めた。
≪ラジカル硬化性ホットメルトウレタン樹脂組成物を用いた光学用成形品1≫
前記で得たラジカル硬化性ホットメルトウレタン樹脂組成物(RHM1)を100℃に加熱溶融させ、100℃に加熱されたナイフコーターを用いて、基材である70μm厚みの離型処理PET上に100μmの厚みで塗布した。次いで、前記塗布面に、装置内を1回通過させるごとに145mJ/cm2の紫外線照射量となるように設定したコンベアタイプの紫外線照射装置CSOT―40(日本電池株式会社製、高圧水銀ランプ使用、強度120W/cm、コンベアスピード5m/分)内を1回通過させることによって紫外線照射(UV照射)を行なった。次いで、温度23℃、相対湿度65%の恒温恒湿槽内で3日間放置することにより、湿気硬化後の光学用成形品1を得た。
本発明のラジカル硬化性ホットメルトウレタン樹脂組成物(RHM1)を用いた光学用成形品1の特性評価結果を第1表に示した。前記光学用成形品1は、UV照射後に表面タックが消失して、適度な柔軟性と、機械的強度、耐久性(耐加水分解性)、耐黄変性などの優れた性能を有していた。
実施例2及び実施例3は、活性水素含有基を有する(メタ)アクリレート化合物(D)としてHEAの使用量を夫々5.9質量部(実施例2)と8.1質量部(実施例3)に変更した以外は、実施例1と同様の操作で行い、本発明のラジカル硬化性ホットメルトウレタン樹脂組成物(RHM2及びRMM3)を得た。
なお、ウレタンプレポリマー(C-1)の有するイソシアネート基総数に対して、前記(メタ)アクリレート化合物(D)としてHEAが反応したNCO基の数の割合〔[OH/NCO]×100(%)〕は、NCO基総数の理論値が75%(実施例2)と100%(実施例3)になるように設定し行なった。
次いで、実施例1と同様の操作で、本発明のラジカル硬化性ホットメルトウレタン樹脂組成物(RHM2及びRHM3)を用いて、硬化後の光学用成形品2及び3を得た。
前記光学用成形品2及び3の評価結果を第1表に示した。光学用成形品2及び3は、UV照射後に表面タックが消失し、適度な柔軟性と、機械的強度、耐久性(耐加水分解性)、耐黄変性などの優れた性能を有していた。
第1表及び第2表の配合に従い、実施例1と同様の反応手順で上記実施例及び比較例を行なった。そこで得たウレタンプレポリマー(C-2)~(C-17)、ホットメルトウレタン(X-4)~(X-48)、及びラジカル硬化性ホットメルトウレタン樹脂組成物(RHM4)~(RHM48)の評価結果を第1表及び第2表に示した。
第1表の配合に従い、実施例1と同様の反応手順で上記実施例を行なった。そこで得たウレタンプレポリマー(C-6)~(C-7)、ホットメルトウレタン(X-29)~(X-32)に、光重合開始剤(Y-2)としてパーロイルTCPを配合したラジカル硬化性ホットメルトウレタン樹脂組成物(RHM29)~(RHM32)の評価結果を第1表に示した。
次いで、前記ラジカル硬化性ホットメルトウレタン樹脂組成物(RHM29~32)を100℃に加熱溶融させ、100℃に加熱されたナイフコーターを用いて、基材である70μm厚みの離型処理PET上に100μmの厚みにて塗布した。次いで、前記塗布面を150℃に加熱した乾燥機中に10分間放置して加熱硬化させた。次いで、温度23℃、相対湿度65%の恒温恒湿槽内で3日間放置することにより、湿気硬化後の光学用成形品29~32を得た。
本発明のラジカル硬化性ホットメルトウレタン樹脂組成物(RHM29~32)を用いた光学用成形品29~32の特性評価結果を第1表に示した。前記光学用成形品29~32は、加熱硬化後に表面タックが消失して、適度な柔軟性と、機械的強度、耐久性(耐加水分解性)、耐黄変性などの優れた性能を有していた。
1,5PD :1,5-ペンタンジオール
1,6HD :1,6-ヘキサンジオール
NPG :ネオペンチルグリコール
DEG :ジエチレングリコール
AA :アジピン酸
TMP :トリメチロールプロパン
HMDI :ジシクロヘキシルメタン-4,4’-ジイソシアネート
BICH :1,3-ビス(イソシアナートメチル)シクロヘキサン
MDI :4,4’-ジフェニルメタンジイソシアネート
IPDI :イソホロンジイソシアネート
XDI :キシリレンジイソシアネート
HEA :2-ヒドロキシエチルアクリレート
4HBA :4-ヒドロキシブチルアクリレート
HEMA :2-ヒドロキシエチルメタクリレート
PTMG-1000:商品名、三菱化学株式会社製、ポリテトラメチレングリコール、Mn=1000のもの。
PTXG-1000:商品名、旭化成繊維株式会社製、ポリテトラメチレングリコール誘導体であり、テトラメチレンエーテルとネオペンチルグリコールとのランダム共重合体からなる鎖状のジオール、Mn=1000のもの。
CHDM :シクロヘキサンジメタノール
SUCA :コハク酸
CHDM/SUCA-1000:シクロヘキサンジメタノールとコハク酸とのポリマー(Mn=1000)
HHPA :ヘキサヒドロ無水フタル酸
DURANOL T-5652:商品名、旭化成ケミカルズ株式会社製、1,5-ペンタンジオールと1,6-ヘキサンジオールを含むポリオールと、ジアルキルカーボネートを反応させて得られるMn=2000の脂肪族ポリカーボネートポリオール。
UC-100:宇部興産株式会社製、シクロヘサンジメタノールとジアルキルカーボネートを反応させて得られるMn1000の脂環式ポリカーボネートポリオール。
イルガキュア651:商品名、チバ・スペシャリティ・ケミカルズ株式会社製、光重合開始剤
イルガキュア184:商品名、チバ・スペシャリティ・ケミカルズ株式会社製、光重合開始剤
パーロイルTCP:商品名、日本油脂株式会社製、パーオキシジカーボネート系過酸化物
Claims (11)
- (メタ)アクリロイル基を有するホットメルトウレタン(X)とラジカル重合開始剤(Y)とを含有するラジカル硬化性ホットメルトウレタン樹脂組成物であって、前記ホットメルトウレタン(X)が、脂肪族ポリカーボネートポリオール(a1)、脂環式ポリカーボネートポリオール(a2)、又は脂肪族ポリエーテルポリオール(a3)を含むポリオール(A)と、脂環式ポリイソシアネート(B)とを反応させて得られるイソシアネート基を末端に有するホットメルトウレタンプレポリマー(C)であり、前記ウレタンプレポリマー(C)が有するイソシアネート基総数の50モル%を超えて100モル%以下を、活性水素含有基を有する(メタ)アクリレート化合物(D)により、(メタ)アクリロイル基を導入させたものであり、且つ、
前記ホットメルトウレタン(X)100質量部とラジカル重合開始剤(Y)0.5~5.0質量部を含有することを特徴とするラジカル硬化性ホットメルトウレタン樹脂組成物。 - 前記脂肪族ポリカーボネートポリオール(a1)が、1,4-ブタンジオール、1,5-ペンタンジオール、及び1,6-ヘキサンジオールから選ばれる少なくとも一種であるか、又は脂環式ポリカーボネートポリオール(a2)が、シクロヘキサンジメタノール又は前記誘導体とジアルキルカーボネートとを反応させて得られるポリオールである請求項1に記載のラジカル硬化性ホットメルトウレタン樹脂組成物。
- 前記脂肪族ポリエーテルポリオール(a3)が、ポリテトラメチレングリコール又はポリテトラメチレングリコール誘導体である請求項1に記載のラジカル硬化性ホットメルトウレタン樹脂組成物。
- 前記ポリオール(A)が全量100質量部中に、前記脂肪族ポリカーボネートポリオール(a1)と前記脂環式ポリカーボネートポリオール(a2)と前記脂肪族ポリエーテルポリオール(a3)との合計量で、20質量部以上を含有するポリオールである請求項1に記載のラジカル硬化性ホットメルトウレタン樹脂組成物。
- 前記ポリオール(A)に、更に脂環式ポリエステルポリオール(a4)を含む請求項1に記載のラジカル硬化性ホットメルトウレタン樹脂組成物。
- 前記脂環式ポリエステルポリオール(a4)が、シクロヘキサン環を有するポリオールである請求項5に記載のラジカル硬化性ホットメルトウレタン樹脂組成物。
- 前記ポリオール(A)が全量100質量部中に、前記脂肪族ポリカーボネートポリオール(a1)又は脂環式ポリカーボネートポリオール(a2)20~95質量部、前記脂肪族ポリエーテルポリオール(a3)20~95質量部、及び前記脂環式ポリエステルポリオール(a4)10~50質量部を含有するポリオールである請求項5に記載のラジカル硬化性ホットメルトウレタン樹脂組成物。
- 前記脂環式ポリイソシアネート(B)が、4,4’-ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート及び1,3-ビス(イソシアナートメチル)シクロヘキサンから選ばれる少なくとも一種のポリイソシアネートである請求項1に記載のラジカル硬化性ホットメルトウレタン樹脂組成物。
- 前記イソシアネート基を末端に有するホットメルトウレタンプレポリマー(C)の100℃における溶融粘度が、500~5000mPa・sである請求項1に記載のラジカル硬化性ホットメルトウレタン樹脂組成物。
- 請求項1~9の何れか一項に記載のラジカル硬化性ホットメルトウレタン樹脂組成物を用いて製造されたことを特徴とする光学用成形体。
- 前記光学用成形体が、導光フィルム、導光シート、導光板、及び導光繊維から選ばれる少なくとも一種の導光用物品である請求項10に記載の光学用成形体。
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2014098178A1 (ja) * | 2012-12-21 | 2014-06-26 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | 湿気硬化型ホットメルト接着剤 |
JP2015063616A (ja) * | 2013-09-25 | 2015-04-09 | Dic株式会社 | 活性エネルギー線硬化性組成物、その硬化塗膜、及び該硬化塗膜を有する物品 |
WO2015098308A1 (ja) * | 2013-12-25 | 2015-07-02 | Dic株式会社 | 紫外線硬化型粘着剤組成物、粘着フィルム、及び、粘着フィルムの製造方法 |
JP2015120773A (ja) * | 2013-12-20 | 2015-07-02 | Dic株式会社 | 接着シート、画像表示装置及びその製造方法 |
WO2015098307A1 (ja) * | 2013-12-25 | 2015-07-02 | Dic株式会社 | 紫外線硬化型粘着剤組成物、粘着フィルム、及び、粘着フィルムの製造方法 |
WO2016043239A1 (ja) * | 2014-09-16 | 2016-03-24 | 株式会社巴川製紙所 | 保護フィルム、フィルム積層体および偏光板 |
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Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2024124372A1 (zh) * | 2022-12-12 | 2024-06-20 | 万华化学集团股份有限公司 | 聚氨酯胶黏剂、无醛添加模压托盘及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008169319A (ja) * | 2007-01-12 | 2008-07-24 | Dic Corp | 接着剤用硬化型樹脂組成物 |
JP2010180328A (ja) * | 2009-02-05 | 2010-08-19 | Inoac Corp | 導光体形成用組成物及び導光シート |
JP2011208097A (ja) * | 2010-03-30 | 2011-10-20 | Dainippon Printing Co Ltd | 電子線硬化性樹脂組成物、及びそれを用いてなる積層体 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5426166A (en) * | 1994-01-26 | 1995-06-20 | Caschem, Inc. | Urethane adhesive compositions |
JP2001040061A (ja) | 1999-07-27 | 2001-02-13 | Hitachi Kasei Polymer Co Ltd | 光硬化性樹脂組成物 |
JP2001040062A (ja) | 1999-07-27 | 2001-02-13 | Hitachi Kasei Polymer Co Ltd | 光硬化性樹脂組成物 |
JP2005002309A (ja) | 2003-04-18 | 2005-01-06 | Hiroshi Okai | 2剤型反応性ホットメルト硬化性組成物及びその製造方法並びに混合方法 |
JP2005248019A (ja) | 2004-03-04 | 2005-09-15 | Sumitomo Bakelite Co Ltd | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 |
JP4269073B2 (ja) | 2004-03-11 | 2009-05-27 | 岡井 洋 | 反応性ホットメルト硬化性組成物及び硬化方法 |
JP4482463B2 (ja) | 2005-02-01 | 2010-06-16 | 日本ユピカ株式会社 | ラジカル硬化性樹脂組成物 |
JP5534125B2 (ja) * | 2007-10-30 | 2014-06-25 | スリーボンドファインケミカル株式会社 | 硬化性シート組成物 |
JP2010037380A (ja) | 2008-08-01 | 2010-02-18 | Teijin Chem Ltd | 導光板用芳香族ポリカーボネート樹脂組成物及び導光板 |
JP4983935B2 (ja) | 2010-01-29 | 2012-07-25 | 横浜ゴム株式会社 | 硬化性樹脂組成物 |
-
2011
- 2011-12-21 JP JP2012524970A patent/JP5126455B1/ja active Active
- 2011-12-21 CN CN201180026681.3A patent/CN102933629B/zh active Active
- 2011-12-21 KR KR1020127030626A patent/KR101798089B1/ko active IP Right Grant
- 2011-12-21 US US13/809,266 patent/US9018319B2/en active Active
- 2011-12-21 WO PCT/JP2011/079626 patent/WO2012096111A1/ja active Application Filing
-
2012
- 2012-01-12 TW TW101101177A patent/TWI433862B/zh active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008169319A (ja) * | 2007-01-12 | 2008-07-24 | Dic Corp | 接着剤用硬化型樹脂組成物 |
JP2010180328A (ja) * | 2009-02-05 | 2010-08-19 | Inoac Corp | 導光体形成用組成物及び導光シート |
JP2011208097A (ja) * | 2010-03-30 | 2011-10-20 | Dainippon Printing Co Ltd | 電子線硬化性樹脂組成物、及びそれを用いてなる積層体 |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014122299A (ja) * | 2012-12-21 | 2014-07-03 | Henkel Japan Ltd | 湿気硬化型ホットメルト接着剤 |
WO2014098178A1 (ja) * | 2012-12-21 | 2014-06-26 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | 湿気硬化型ホットメルト接着剤 |
JP2015063616A (ja) * | 2013-09-25 | 2015-04-09 | Dic株式会社 | 活性エネルギー線硬化性組成物、その硬化塗膜、及び該硬化塗膜を有する物品 |
JP2015120773A (ja) * | 2013-12-20 | 2015-07-02 | Dic株式会社 | 接着シート、画像表示装置及びその製造方法 |
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WO2015098307A1 (ja) * | 2013-12-25 | 2015-07-02 | Dic株式会社 | 紫外線硬化型粘着剤組成物、粘着フィルム、及び、粘着フィルムの製造方法 |
JP5822052B1 (ja) * | 2013-12-25 | 2015-11-24 | Dic株式会社 | 紫外線硬化型粘着剤組成物、粘着フィルム、及び、粘着フィルムの製造方法 |
JP5822051B1 (ja) * | 2013-12-25 | 2015-11-24 | Dic株式会社 | 紫外線硬化型粘着剤組成物、粘着フィルム、及び、粘着フィルムの製造方法 |
US10377915B2 (en) * | 2014-06-04 | 2019-08-13 | Corning Incorporated | Optical fiber coating and composition |
US20180327625A1 (en) * | 2014-06-04 | 2018-11-15 | Corning Incorporated | Optical fiber coating and composition |
WO2016043239A1 (ja) * | 2014-09-16 | 2016-03-24 | 株式会社巴川製紙所 | 保護フィルム、フィルム積層体および偏光板 |
JP2017043697A (ja) * | 2015-08-27 | 2017-03-02 | Dic株式会社 | 電子機器用封止材、及び、電子機器 |
TWI625542B (zh) * | 2016-04-12 | 2018-06-01 | Lg化學股份有限公司 | 用於光學用途的黏著劑組成物 |
WO2019221126A1 (ja) * | 2018-05-16 | 2019-11-21 | 宇部興産株式会社 | 光硬化性樹脂組成物及びそれを用いた粘接着剤 |
JP2020002261A (ja) * | 2018-06-28 | 2020-01-09 | Dic株式会社 | 湿気硬化型ポリウレタンホットメルト樹脂組成物 |
JP7196434B2 (ja) | 2018-06-28 | 2022-12-27 | Dic株式会社 | 湿気硬化型ポリウレタンホットメルト樹脂組成物 |
JP2020094123A (ja) * | 2018-12-12 | 2020-06-18 | Dic株式会社 | 湿気硬化型ウレタンホットメルト樹脂組成物、及び、積層体 |
JP2020094124A (ja) * | 2018-12-12 | 2020-06-18 | Dic株式会社 | 湿気硬化型ウレタンホットメルト樹脂組成物、及び、積層体 |
JP7139928B2 (ja) | 2018-12-12 | 2022-09-21 | Dic株式会社 | 湿気硬化型ウレタンホットメルト樹脂組成物、及び、積層体 |
JP7172542B2 (ja) | 2018-12-12 | 2022-11-16 | Dic株式会社 | 湿気硬化型ウレタンホットメルト樹脂組成物、及び、積層体 |
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