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GB2163443A - Photocurable resin composition - Google Patents

Photocurable resin composition Download PDF

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Publication number
GB2163443A
GB2163443A GB08517046A GB8517046A GB2163443A GB 2163443 A GB2163443 A GB 2163443A GB 08517046 A GB08517046 A GB 08517046A GB 8517046 A GB8517046 A GB 8517046A GB 2163443 A GB2163443 A GB 2163443A
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GB
United Kingdom
Prior art keywords
acrylate
group
resin composition
photocurable resin
methacrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB08517046A
Other versions
GB2163443B (en
GB8517046D0 (en
Inventor
Toshinobu Takahashi
Hidekazu Takeyama
Shigeo Omote
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yokohama Rubber Co Ltd
Original Assignee
Yokohama Rubber Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yokohama Rubber Co Ltd filed Critical Yokohama Rubber Co Ltd
Publication of GB8517046D0 publication Critical patent/GB8517046D0/en
Publication of GB2163443A publication Critical patent/GB2163443A/en
Application granted granted Critical
Publication of GB2163443B publication Critical patent/GB2163443B/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/106—Single coatings
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)

Abstract

A photocurable resin composition comprises (a) 20 to 80 wt% of urethane acrylate having acryloyl groups or methacryloyl groups at both ends, and (b) 80 to 20 wt% of monofunctional acrylate represented by the following formula (1) or (2), said urethane acrylate being obtained by reacting diisocyanate with both ends of polytetramethylene glycol having a molecular weight greater than 850, and then reacting the reaction product with a compound having an acryloyl group or methacryloyl group and a hydroxyl group: <IMAGE> [where R is an alkyl group (C6H13 - C18H37) and R1 is H or CH3], <IMAGE> where n is an integer of 1 to 14; R2 is an alkyl group, phenyl group, alicyclic group, or heterocyclic group; and R3 is H or CH3). The composition is suitable for forming the primary coating on optical fibres.

Description

SPECIFICATION Photocurable resin composition The present invention relates to a photocurable resin composition which is suitable for the primary coating on optical fiber.
The optical fiber is made up of a glass or plastic fiber core and a protective layer covering the core. The fiber core is composed of core and cladding, each having a different refractive index, so that it transmits light from one end to the other without light scattering. This characteristic property is applied to optical communications which are being put to practical use.
Heretofore, the protective layer of optical fiber has been composed of two layers. One is a soft primary layer which is in direct contact with the outer surface ofthe optical fiber, and the other is a hard secondary layer placed on the primary layer. These layers are usually made of synthetic resin.
The material from which the primary coating layer is made should have the following characteristic properties. (1) A glass transition point (Tg) lower than normal temperature which should be as low as possible. This is necessary in orderforthe primary layerto be flexible at normal temperature and to have shock-absorbing properties. (2) A tensile modulus lower than 1.0 kg/cm2, preferably lower than 0.5 kg/cm2.
This is necessaryforthe primarylayerto have shock-absorbing properties. (3) Good resistance to aging by heat and warm water (wet heat). This is necessary because the optical fiber is laid on the bottom of the sea or in soil for a long period of time, and the protective layer should retain the initial physical properties (such as tensile strength and elongation at break). (4) an elongation at break greater than 10%, preferably greater than 20%. This is necessary because the optical fiber is often bent in use and the protective layer should be flexible enough for bending.
The conventionally used material for the primary coating lacks the above-mentioned characteristic properties. Moreover, it cures slow when the primary coating layer is formed on the optical fiber, and this leads to low productivity.
It is an object of this invention to provide a photocurable resin composition which is suitable for the primary coating on optical fiber because of its low glass transition temperature (Tg), low elastic modulus, and good resistance to aging by heat and warm water.
The gist of this invention resides in a photocurable resin composition which comprises (a) 20 to 80 wt% of urethane acrylate having acryloyl groups or methacryloyl groups at both ends, and (b) 80 to 20 wt% of monofunctional acrylate represented by the following formula (1) or (2), the urethane acrylate being obtained by reacting diisocyanate with both ends of polytetramethylene glycol having a molecular weight greater than 850, and then reacting the reaction product with a compound having an acryloyl group or methacryloyl group and a hydroxyl group:
[where R is an alkyl group (C6H13 - C18H37) and R1 is H or CH3J,
(where n is an integer of 1 to 14; R1 is H or CH3; R2 is an alkyl group, phenyl group, alicyclic group, or heterocyclic group; and R3 is H or CH3).
These and other objects of this invention will become more apparent in the detailed description and examples which follow.
The constitution of the invention is described in detail in the following.
(a) Urethane acrylate having acryloyl groups or methacryloyl groups at both ends: This compound is obtained by reacting diisocyanate with both ends of polytetramethylene glycol (abbreviated as PTMG hereinafter) having a molecular weight greater than 850, and then reacting the reaction product with a compound having an acryloyl group or methacryloyl group and a hydroxyl group. The reactions may be carried out in the usual way.
PTMG having a high molecular weight is preferable to give the resin composition having a low elastic modulus. Thus PTMG should have a molecular weight greater than 850, preferably 1000 to 10,000.
The diisocyanate used in the reaction may be a commercial one such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated MDI, and isophorone diisocyanate (IPDI).
The compound having an acryloyl group or methacryloyl group and a hydroxyl group includes, for example, 2-hydroxyethyl acrylate (2-HEA), 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. They are not limitative. Acrylate rather than methacrylate is preferred from the standpoint of the curing rate of the resulting resin composition.
(b) Monofunctional acrylate: This compound is represented by the formula (1) or (2) shown above. As the carbon number of R in the formula (1) decreases, the monofunctional acrylate is more volatile and the resulting resin composition yields a cured product having a high glass transition temperature. This is not preferable. Thus the carbon number of R should be 6 to 18 in this invention. Incidentally, R is an alkyl group having a branched structure.
Examples of the monofunctional acrylate represented by the formula (1) include 2-ethylhexyl acrylate, 2 ethylhexyl methacrylate, undecyl acrylate, undecyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, and stearyl methacrylate.
Examples of the monofunctional acrylate represented by the formula (2) include butoxyethyl acrylate, butoxyethyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxypropyl acrylate, phenoxypropyl methacrylate, butoxydiethyleneglycol monoacrylate, and polyethylene glycol monoacrylate (n = 4, 9, 14, etc.). Further, when R2 in formula (2) is an alkyl group, it preferably contains from 1 to 18 carbon atoms.
The monofucntional acrylate functions as a diluent of the urethane acrylate which is a highly viscous liquid or waxlike solid, so that the resulting resin composition has a desired viscosity for coating operation. It also controls the elastic modulus of the cured product. In other words, urethane acrylate is not good in workability when used alone, and it affords, when used alone, a curred product having a high elastic modulus beyond the upper limit on account of its difunctionality.
(c) The photocurable resin composition of this invention is composed of 20 to 80 wt% of the urethane acrylate and 80 to 20 wt% of the monofunctional acrylate.
If the content of urethane acrylate is less than 20 wt% and the content of monofunctional acrylate is more than 80 wt%, the resulting cured product has a low elastic modulus and is very soft, but has a tacky surface.
Conversely, if the content of urethane acrylate is more than 80 wt% and the content of monofunctional acrylate is less than 20 wt%, the resulting resin composition is so viscous that the workability is poor, and the cured product has a high elastic modulus.
The photocurable resin composition of this invention may be incorporated with other additives such as photosensitizer, cure accelerator, internal release agent, adhesion promotor, transparent filler, anti-sag agent, dispersing agent, and polymerization inhibitor.
The photocurable resin composition of this invention which is composed of 20 to 80 wt% of urethane acrylate and 80 to 20 wt% of monofunctional acrylate as mentioned above, produces the following effects.
(i) The composition has a low glass transition point (Tg) and a low elastic modulus and is superior in resistance to aging by heat and warm water. Thus it is suitable for the primary coating on optical fiber.
(ii) The composition cures rapidly upon exposure to light, and this contributes to the improvement of productivity of covered optical fibers.
The invention is now described with reference to the following examples and comparative examples.
Examples and comparative examples (1) Synthesis of urethane acrylate: PTMG and diisocyanate were heated at 800 C for 4 hours so that the diisocyanate reacts with the terminals of PTMG. Then, the reaction product and 2-hydroxyethyl acrylate (2-HEA) were heated at 80" C for 6 hours so that 2-HEA reacts with the terminals of the reaction product. Thus there was obtained the desired urethane acrylate. The details of the reactants are given in the note to Table 1.
(2) The urethane acrylate was mixed with a monofunctional acrylate which had been incorporated with a photosensitizer shown in Table 1. After thorough mixing, there was obtained a UV-curable resin composition. This resin composition was exposed to ultraviolet rays, 15 J/cm2, from a UV lamp (80 W/cm, 1 kW multimetal lamp). Thus there was obtained a 1 mm thick cured sheet.
Rectangular test pieces each measuring 1 x 7 cm and dumbbell specimens (JIS No. 1) were prepared from the sheet. The rectangular test pieces were used for the measurement of glass transition point The torsionai elastic modulus of the test piece was measured at varied temperatures according to the TBA method (torsional braid analysis), and the glass transition point was calculated from the peak value of tan ô.
Tensile modulus, tensile strength, and elongation at break were measured by using the JIS No. 1 dumbbell specimens at a pulling rate of 10 mm/min.
Resistance to aging by heat was evaluated by measuring tensile properties after aging in an oven at 80"C for i month. Resistance to aging by warm water was evaluated by measuriMensile properties after aging in warm water at 80" C for 1 month. Resistance to aging in Table 1 is expressed in terms of retention of property values measured after aging compared with the original ones. Values in Table 1 are parts by weight unless otherwise indicated.
(3) In Comparative Example 1, a photocurable resin composition was prepared in the same manner as above, except that PTMG was replaced by polypropylene glycol (PPG) having a molecular weight of 2000 and the diisocyanate was replaced by MDI. The resulting resin composition was examined in the same way as mentioned above.
TABLE 1 Example No. 1 2 3 4 5 6 7 8 1* A 20 50 B 50 C 50 50 50 50 80 D 50 E 50 F 80 50 G 50 50 50 H 50 50 50 Photosensitizer 2 2 2 2 2 2 2 2 2 -17 -10 -15 -22 -20 -45 -20 -22 -25 Tg ( C) Tensile modulus (kg/cm) 0.1 0.7 0.5 0.3 0.3 0.2 0.2 0.9 0.3 Tensile strength 8.1 42.5 35.0 22.0 20.9 16.5 17.5 47.3 16.8 Elongation at break (%) 65 67 82 78 70 78 82 60 85 Resistance to aging by heating (retention after 1 month at 80 C) Tensile modulus (kg/cm) 78 120 117 115 91 111 81 93 60 Tensile strength (kg/cm) 84 111 113 109 84 105 76 103 42 Elongation at break (%) 79 78 82 80 87 123 96 104 64 Resistance to aging by warm water (retention after 1 month at 80 C) Tensile modulus (kg/cm) 71 105 119 109 82 105 80 90 30 Tensile strength (kg/cm) 84 101 104 103 77 87 74 85 58 Elongation at break (%) 72 85 94 105 82 76 80 94 210 * Comparative Example Note to Table 1.
Urethane Acrylate: A: Prepared by reacting 850 g of PTMG (MW 850) with 520 g of MDI and then with 233 g of 2-HEA.
B : Prepared by reacting 650 g of PTMG (MW 1300) with 251 g of MDI and then with 117 g of 2-HEA.
C: Prepared by reacting 1000 g of PTMG (MW 2000) with 263 g of hydrogenated MDI and then with 117 g of 2-HEA.
D: Prepared by reacting 1000 g of PTMG (MW 2000) with 251 g of MDI and then with 117 g of 2-HEA.
Monofunctional acrylate: E: One represented by the formula (1) wherein R is CH2CH(C2H5)C4Hg and R1 is CH3.
F : One represented by the formula (1) wherein R is C12H25 and Ra is H.
G : One represented by the formula (2) wherein n is 1, R1 is H, R2 is C4H9, and R3 is H.
H : One represented by the formula (2) wherein n is 4, R1 is H, R2 is phenyl, and R3 is H.
Photosensitizer: 1-hydroxycyclohexyl benzophenone As is apparent from Table 1 the resin compositions in Examles 1 to 8 in which urethane acrylate was prepared from PTMG are superior in aging resistance to the one in Comparative Example 1 in which urethane acrylate was prepared from PPG. As the molecular weight of PTMG decreases, the resulting resin composition increases in elastic modulus; thus the lower limit of the molecular weight is 850. (See Examples 2 to 4.) With PTMG having a molecular weight of 2000, the resulting resin composition has the lowest elastic modulus. (See Examples 4 to 8.) The upper limit of the monofunctional acrylate is 80 wt% (as in Example 1), and beyond this limit, the resulting cured product is excessively soft and has a tacky surface. The upper limit of the urethane acrylate is 80 wt% (as in Example 8), and beyond this limit, the resulting resin composition has an excessively high elastic modulus

Claims (7)

1. A photocurable resin composition which comprises (a) 20 to 80 wt% of urethane acrylate having acryloyl groups or methacryloyl groups at both ends, and (b) 80 to 20 wt% of monofunctional acrylate represented by the following formula (1) or (2), said urethane acrylate being obtained by reacting diisocyanatewith both ends of polytetramethylene glycol having a molecularweightgreaterthan 850, and then reacting the reaction product with a compound having an acryloyl group or methacryloyl group and a hydroxyl group:
[where R is an alkyl group (C6H13- C18H37) and R1 is H or CH3],
(where n is an integer of 1 to 14; R1 is H or CH3; R2 is an alkyl group, phenyl group, alicyclic group, or heterocyclic group; and R3 is H or CH2).
2. A photocurable resin composition as claimed in claim 1, wherein the polytetramethylene glycol is one which has a molecular weight of 100 to 10,000.
3. A photocurable resin composition as claimed in claim 1 or 2, wherein the diisocyanate is tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, or isophorone diisocyanate.
4. A photocurable resin composition as claimed in anyone of claims 1 to 3, wherein the compound having an acryloyl group or methacryloyl group is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, or 2-hydroxypropyl methacrylate.
5. A photocurable resin composition as claimed in anyone of claims 1 to 4, wherein the monofunctional acrylate is 2-ethylhexyl acrylate, 2-ethyihexyl methacrylate, undecyl acrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxypropyl acrylate, phenoxypropyl methacrylate, butoxydiethylene glycol monoacrylate, or polyethylene glycol monoacrylate.
6. A photocurable resin composition as claimed in anyone of claims 1 to 5, which further comprises one or more of photosensitizer, cure accelerator, internal release agent, adhesion promotor, transparent filler, anti-sag agent, dispersing agent, and polymerization inhibitor.
7. A photocurable resin composition, substantially as described in any of the foregoing Examples.
GB08517046A 1984-07-10 1985-07-05 Photocurable resin composition Expired GB2163443B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59142996A JPS6121117A (en) 1984-07-10 1984-07-10 Photosetting resin composition

Publications (3)

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GB8517046D0 GB8517046D0 (en) 1985-08-14
GB2163443A true GB2163443A (en) 1986-02-26
GB2163443B GB2163443B (en) 1988-04-20

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KR (1) KR860001143A (en)
GB (1) GB2163443B (en)

Cited By (20)

* Cited by examiner, † Cited by third party
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GB2194951A (en) * 1986-09-10 1988-03-23 Courtaulds Plc Production of urethane polymer films
EP0260842A2 (en) * 1986-09-10 1988-03-23 Imperial Chemical Industries Plc Coating compositions
GB2195643A (en) * 1986-07-21 1988-04-13 Yokohama Rubber Co Ltd Uv curable urethane acrylate composition
EP0277813A2 (en) * 1987-02-04 1988-08-10 MITSUI TOATSU CHEMICALS, Inc. Photosetting resin composition
GB2204049A (en) * 1987-04-21 1988-11-02 Gore & Ass Radiation curable compositions for hydrophilic coatings
EP0301733A1 (en) * 1987-07-21 1989-02-01 MITSUI TOATSU CHEMICALS, Inc. Photocuring resin compositions
US4912185A (en) * 1986-11-21 1990-03-27 Sola International Holdings Ltd. Cross-linkable casting compositions
GB2226566A (en) * 1988-12-12 1990-07-04 Croda Applic Chemicals Limited Coating composition for use in automotive sealing process
EP0490981A1 (en) * 1989-09-06 1992-06-24 Desoto Inc Primary coatings for optical glass fibers including polyether acrylates.
WO1995014720A1 (en) * 1993-11-26 1995-06-01 Henkel Kommanditgesellschaft Auf Aktien Aerobic adhesive
WO1996011965A1 (en) * 1994-10-14 1996-04-25 Dsm N.V. Optical glass fiber coating composition
WO1998039374A1 (en) * 1997-03-07 1998-09-11 Dsm N.V. Radiation-curable composition having high cure speed
EP0874012A1 (en) * 1997-04-25 1998-10-28 Takeda Chemical Industries, Ltd. Coating composition for optical fiber
FR2854956A1 (en) * 2003-05-16 2004-11-19 Nexans Photo-crosslinkable liquid composition for production of plastic fibre, e.g. optical fibre or textile fibre, based on crosslinkable components with acrylate groups rather than methacrylate groups
EP2484731A4 (en) * 2009-09-29 2017-12-27 DIC Corporation Primer composition, waterproof floor slab structure using same, and method for waterproofing floor slab
WO2019103855A1 (en) * 2017-11-22 2019-05-31 3M Innovative Properties Company Photopolymerizable compositions including a urethane component and a monofunctional reactive diluent, articles, and methods
WO2020003169A1 (en) * 2018-06-29 2020-01-02 3M Innovative Properties Company Orthodontic articles comprising cured free-radically polymerizable composition with improved strength in aqueous environment
US11104758B2 (en) 2018-06-29 2021-08-31 3M Innovative Properties Company Orthodontic articles prepared using a polycarbonate diol, and methods of making same
US11225535B2 (en) 2018-06-29 2022-01-18 3M Innovative Properties Company Photopolymerizable compositions including a polyurethane methacrylate polymer prepared using a polycarbonate diol, articles, and methods
US11904031B2 (en) 2017-11-22 2024-02-20 3M Innovative Properties Company Orthodontic articles comprising polymerized composition comprising at least two free-radical initiators

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JPS63130609A (en) * 1986-11-21 1988-06-02 Yokohama Rubber Co Ltd:The Ultraviolet-curable resin composition
JP2627626B2 (en) * 1987-10-20 1997-07-09 日本合成ゴム株式会社 Composition for optical fiber coating
JPH03111087A (en) * 1989-09-25 1991-05-10 Hitachi Ltd Controller for industrial sewing machine
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JP4525825B2 (en) 2006-03-31 2010-08-18 藤倉化成株式会社 Hard coat coating composition for metal substrate
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JP7431526B2 (en) * 2019-07-31 2024-02-15 タキロンシーアイ株式会社 Decorative sheet and its manufacturing method

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Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2195643A (en) * 1986-07-21 1988-04-13 Yokohama Rubber Co Ltd Uv curable urethane acrylate composition
GB2195643B (en) * 1986-07-21 1990-08-15 Yokohama Rubber Co Ltd Uv-curable resin compositions
GB2194951B (en) * 1986-09-10 1990-01-10 Courtaulds Plc Production of urethane polymer films
EP0260842A2 (en) * 1986-09-10 1988-03-23 Imperial Chemical Industries Plc Coating compositions
EP0260842A3 (en) * 1986-09-10 1988-07-20 Imperial Chemical Industries Plc Coating compositions
GB2194951A (en) * 1986-09-10 1988-03-23 Courtaulds Plc Production of urethane polymer films
US4912185A (en) * 1986-11-21 1990-03-27 Sola International Holdings Ltd. Cross-linkable casting compositions
EP0277813A2 (en) * 1987-02-04 1988-08-10 MITSUI TOATSU CHEMICALS, Inc. Photosetting resin composition
EP0277813A3 (en) * 1987-02-04 1989-07-26 MITSUI TOATSU CHEMICALS, Inc. Photosetting resin composition
GB2204049A (en) * 1987-04-21 1988-11-02 Gore & Ass Radiation curable compositions for hydrophilic coatings
AU590483B2 (en) * 1987-07-21 1989-11-02 Mitsui Toatsu Chemicals Inc. Photocuring resin compositions
EP0301733A1 (en) * 1987-07-21 1989-02-01 MITSUI TOATSU CHEMICALS, Inc. Photocuring resin compositions
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GB2163443B (en) 1988-04-20
JPS6121117A (en) 1986-01-29
KR860001143A (en) 1986-02-22
GB8517046D0 (en) 1985-08-14

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