JP2002128754A - Urethane compound, its resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition providing a cured product having antistatic performances, scarcely sticking dust and having good wet-heat resistance. SOLUTION: This resin composition comprises (A) a urethane compound which is a reactional product of (a) a bis(2-hydroxyethyl)taurine quaternary ammonium salt with (b) 2-isocyanatoethyl methacrylate and (B) an unsaturated group-containing compound other than the component (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane compound and a resin composition which are cured by an active energy ray, and a cured product thereof. The present invention relates to a resin composition and a cured product that can be suitably used as a protective coating agent having a protective ability or a hard coating agent for preventing scratches on an optical disc.

[0002]

2. Description of the Related Art Polycarbonate is used as a substrate of a digital audio disk, an optical disk, and a magneto-optical disk for recording and reproducing information on an optical recording layer comprising a recording layer or a light reflecting layer, and reproducing information formed on the information recording layer. A synthetic resin substrate such as amorphous polyolefin is used.

[0003] These resins are optically homogeneous and have high transparency, and are excellent in moldability and mechanical strength. However, their surface hardness is low, and the substrate surface is easily scratched. This has the disadvantage that the read sensitivity of the information recorded on the disc is reduced and errors are likely to occur.

Further, the synthetic resin substrate is liable to be charged when used, and is liable to adsorb dust and dirt on the surface thereof, which also has the disadvantage that the signal reading sensitivity is lowered and an error occurs.

[0005] In order to solve such problems, a resin composition curable by light or heat is applied to a synthetic resin substrate, and a surface protective coating agent for protecting the substrate by curing the resin composition has been developed. I have.

Further, in order to prevent the charging property of the substrate,
Protective coating agents are required to have antistatic ability, but methods such as adding an antistatic agent to the protective coating agent cause bleeding of the antistatic agent on the disk surface, which poses a problem with long-term stability. is there.

Therefore, there is a need for a protective coating agent which has an antistatic function for preventing the attachment of dust while protecting the substrate surface and for forming a protective coat having excellent long-term stability.

[0008]

DISCLOSURE OF THE INVENTION The present invention relates to a resin composition and a cured product which are excellent in scratch resistance, have an antistatic property, are cured uniformly, and are used for forming protective coats on various substrate surfaces. To submit. Particularly preferred is to provide an optical disk material and a cured product for forming a protective coat having excellent long-term stability on the disk surface.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, by using a specific urethane compound (A), a resin having a desired function has been obtained. The present inventors have found that a composition and a cured product thereof can be obtained, and have completed the present invention. That is, the present invention provides (1) a urethane compound (A) which is a reaction product of a quaternary ammonium salt of bis (2-hydroxyethyl) taurine (a) and 2-isocyanatoethyl methacrylate (b). (2) Urethane compound (A) according to item (1)
And a resin composition containing an unsaturated group-containing compound (B) other than the component (A), (3) a resin composition according to the item (2) containing a photopolymerization initiator (C), and (4) an optical disk. The resin composition according to (2) or (3), which is a material for use,
(5) A cured product of the resin composition according to any one of (2) to (4).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The urethane compound (A) of the present invention
Is obtained by reacting bis (2-hydroxyethyl) taurine quaternary ammonium salt (a) with 2-isocyanatoethyl methacrylate (b).

Specific examples of the bis (2-hydroxyethyl) taurine quaternary ammonium salt (a) include, for example,
N, N-bis (2-hydroxyethyl) aminoethanesulfonic acid tetramethylammonium salt, N, N-bis (2-hydroxyethyl) aminoethanesulfonic acid tetraethylammonium salt, N, N-bis (2-hydroxyethyl) Examples thereof include an alkyl ethane (optionally having a benzene ring or another substituent) having 4 to 30 carbon atoms, such as benzyltriethylammonium aminoethanesulfonate.

2-isocyanatoethyl methacrylate (b) can be easily obtained from the market. For example, a product name, Karenz MOI, etc., manufactured by Showa Denko KK can be used.

The urethane compound (A) of the present invention can be prepared, for example, as follows. Bis (2-hydroxyethyl) taurine quaternary ammonium salt (a) 1
It is preferable to react 1 to 2 mol of 2-isocyanatoethyl methacrylate (b) with respect to the mol. The reaction temperature is usually from room temperature to 100 ° C, preferably from 50 to 90 ° C.
It is. In order to prevent gelation due to radical polymerization during this reaction, it is usually preferable to add 50 to 2000 ppm of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, P-methoxyphenol, and P-benzoquinone. The reaction between the hydroxyl group and the isocyanate group proceeds without a catalyst. For example, a catalyst such as dibutyltin laurate or dibutyltin diacetate may be added.

Specific examples of the unsaturated group-containing compound (B) other than the component (A) include, for example, N-vinylpyrrolidone, N-vinylcaprolactone, N, N-dimethylamino (meth) acrylamide, acryloylmorpholine,
Examples include various (meth) acrylate monomers, oligomers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polybutadiene (meth) acrylate.

[0015]

Various acrylate monomers are roughly classified into monofunctional acrylate monomers and polyfunctional acrylate monomers. Monofunctional acrylates are compounds having one acrylate group, for example, phenoxyethyl (meth)
Acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyloxyethyloxyethyl (meth) acrylate, isobonyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, carbitol (Meth) acrylate, acryloylmorpholine, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypo Propylene glycol (meth) acrylate, a half-esters and the like obtained by reacting an acid anhydride of the hydroxyl group-containing (meth) acrylate and a polycarboxylic acid compound. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 1,4-butanediol mono (meth) acrylate. Examples of the acid anhydride of the polycarboxylic acid compound include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and the like.

The polyfunctional acrylate monomers are compounds having two or more acrylate groups, for example, ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A
Di (meth) acrylate, ethylene oxide-modified bisphenol F di (meth) acrylate, 1,4-butanediol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, neopentyl glycol di (meth) hydrivapivalate Acrylate, capullactone-modified neopentyl glycol dihydroxypivalate di (meth) acrylate polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycerin polypropoxytri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol and ε-
Caprolactone reactant poly (meth) acrylate,
Examples include dipentaerythritol poly (meth) acrylate, and epoxy (meth) acrylate which is a reaction product of a mono- or polyglycidyl compound and (meth) acrylic acid. Mono- or polyglycidyl compounds include, for example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6
-Hexanediol diglycidyl ether, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether and the like.

Specific examples of the urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate oligomers include, as urethane (meth) acrylate, a polyol compound (I) and a polyisocyanate compound (II). A reaction product of a hydroxyl group-containing (meth) acrylate (III) can be exemplified. Examples of the polyol compound (I) include an alkyl polyol, a polyester polyol, a polyether polyol, an acrylic polyol, a polybutadiene polyol, a phenolic polyol, and / or a flame-retardant polyol.

As the alkyl polyol, for example, 1,
4-butanediol, 1,6-hexanediol, 1,
8-octanediol, neopentyl glycol, cyclohexanedimethanol, trimethylolpropane, pentaerythritol, and the like.

Examples of the polyester polyol include a condensation type polyester polyol, an addition polymerization polyester polyol, and a polycarbonate polyol. The condensation type polyester polyol is obtained by, for example, a condensation reaction of a diol compound and an organic polybasic acid such as adipic acid, isophthalic acid, terephthalic acid, and sebacic acid, and preferably has a molecular weight of 100 to 100,000. As the diol compound, for example, ethylene glycol, propylene glycol, diethylene glycol,
1,4-butanediol, neopentyl glycol,
Examples thereof include 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,4-hexanedimethanol, dimer acid diol, and polyethylene glycol.

The addition-polymerized polyester polyol includes, for example, polycaprolactone, and has a molecular weight of 1
00 to 100,000 is preferred. Polycarbonate polyol is synthesized by direct phosgenation of polyol, transesterification with diphenyl carbonate, and the like, and preferably has a molecular weight of 100 to 100,000.

Examples of the polyether polyol include PEG (polyethylene glycol), PPG (polypropylene glycol) and PTG (polytetramethylene glycol) polyols. The PEG-based polyol is obtained by subjecting ethylene oxide to addition polymerization using a compound having active hydrogen as a reaction initiator, and preferably has a molecular weight of 100 to 100,000.

The PPG-based polyol is obtained by subjecting propylene oxide to addition polymerization using a compound having active hydrogen as a reaction initiator, and has a molecular weight of 100 to 100,000.
Is preferred. The PTG-based polyol is synthesized by cationic polymerization of tetrahydrofuran and has a molecular weight of 100 to
100,000 is preferred.

Examples of polyether polyols other than the above polyether polyols include bisphenol A ethylene oxide adducts and propylene oxide adducts, and the molecular weight is preferably 100 to 100,000.

Other polyols include (meth) acryl polyols, which are copolymers of (meth) acrylates containing hydroxyl groups and other (meth) acrylates, and copolymers of butadiene with hydroxyl groups at the terminals. A homo- or copolymer having a polybutadiene polyol, a silicon-modified polyol, a phenolic polyol containing a phenol molecule in the molecule,
Epoxy polyols, flame-retardant polyols containing a phosphorus atom, a halogen atom, etc., and the like, having a molecular weight of 100
00,000 is preferred. These polyol compounds,
They can be used alone or in combination of two or more.

Examples of the polyisocyanate compound (II) include 2,4- and / or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), polymeric MDI, 1,5-naphthylene diisocyanate, and trizine. Diisocyanate, 1,6
-Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate (XDI), hydrogenated XD
I, hydrogenated MDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate and the like. These polyisocyanate compounds can be used alone or in combination of two or more.

Hydroxyl-containing (meth) acrylate (II)
I) includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate,
Glycerol diacrylate and the like can be mentioned. They can be used alone or in combination of two or more.

As the epoxy (meth) acrylate,
For example, bisphenol A type epoxy resin (eg, manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1001, 1002,
1004, 1006, etc.), bisphenol F type resin (eg, Yuka Shell Epoxy Co., Ltd., Epicoat 80)
7, EP-4001, EP-4002, EP-4004
Etc.), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg, Yuka Shell Epoxy Co., Ltd.)
YX-4000), phenol novolak type epoxy resin (eg, Nippon Kayaku Co., Ltd., EPPN-201, Yuka Shell Epoxy Co., Ltd., EP-152, EP-154,
Dow Chemical Co., Ltd., DEN-438), cresol novolak type epoxy resin (eg, Nippon Kayaku Co., Ltd., E
OCN-102S, EOCN-1020, EOCN-1
04S), triglycidyl isocyanurate (eg, TEPIC manufactured by Nissan Chemical Co., Ltd.), trisphenol methane type epoxy resin (eg, Nippon Kayaku Co., Ltd., EPPN-5)
01, EPPN-502, EPPN-503), fluorene epoxy resin (eg, Nippon Steel Chemical Co., Ltd., cardo epoxy resin, ESF-300), alicyclic epoxy resin (eg, Daicel Chemical Industries, Ltd.) , Celoxide 202
(P, celloxide EHPE) and (meth) acrylic acid.

Examples of the polyester (meth) acrylate include a condensate of the same polyol compound as the above-mentioned polyol compound and (meth) acrylic acid.

As the polybutadiene (meth) acrylate, a condensate of a liquid polybutadiene compound having a terminal hydroxyl group and (meth) acrylic acid, or a reaction between the liquid polybutadiene compound having a terminal hydroxyl group and the above polyisocyanate compound, Compounds obtained by reacting the same hydroxyl group-containing (meth) acrylate with the same (meth) acrylate can be used. Examples of the photopolymerization initiator (C) include benzophenone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4-benzoyl-4′-methyldiphenylsulfide, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-
Phenyl-ketone, benzyldimethylketal, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)
-Phenylphosphine oxide and the like. Further, a photopolymerization accelerator can be used in combination. Examples of the photopolymerization accelerator include amines such as N, N-dimethylaminobenzoic acid ethyl ester and N, N-dimethylaminobenzoic acid isoamyl ester. These photopolymerization initiators can be used alone or as a mixture of two or more kinds in an arbitrary ratio.

Urethane compound (A) used in the present invention
Is preferably 1 to 30% by weight, particularly preferably 3 to 20% by weight in the composition. The amount of the unsaturated group-containing compound (B) in the composition is preferably 70 to 99% by weight, particularly preferably 80 to 97% by weight. The amount of the photopolymerization initiator (C) is preferably from 0 to 15% by weight, particularly preferably from 0 to 7% by weight.

The resin composition of the present invention comprises each component (A),
It can be obtained by uniformly mixing and dissolving the components (B) and (C). In the composition of the present invention, a silane coupling agent, a polymerization inhibitor, a leveling agent, a slip agent, a light stabilizer, an antioxidant, an organic solvent filler, a coloring agent, and the like can be further used.

The cured product of the composition of the present invention can be obtained by ultraviolet irradiation in a conventional manner. Specifically, for example,
It can be obtained by irradiating ultraviolet rays using a low-pressure or high-pressure mercury lamp, a xenon lamp, or the like. The composition of the present invention is particularly useful as a material for optical disks such as a protective coating agent for optical disks and a hard coating agent for optical disks, but can also be used as a coating material for plastics, rubber, paper, wood and ceramics. . The protective film of the recording film of the optical disk using the optical disk material of the present invention is formed by applying the optical disk material on the recording film of the optical disk by, for example, a spin coating method, and irradiating ultraviolet rays to cure the material. A protective film is formed. When an optical disc material is applied on the recording film of the optical disc, the thickness is usually 1
It is preferably about 100 μm. In these methods, the curing of the composition, particularly the material for an optical disk, can be performed by electron beam irradiation instead of ultraviolet irradiation. A polymerization initiator is not required for electron beam irradiation.

[0034]

EXAMPLES The present invention will be described more specifically with reference to the following examples. Parts in Examples are parts by weight. (Synthesis Example of Urethane Compound (A)) Synthesis Example 1 Bis (2-hydroxyethyl) aminoethylsulfonic acid benzyltriethylammonium salt (molecular weight 404.
6) 404.6 parts, 310 parts of 2-isocyanatoethyl methacrylate (molecular weight: 155) and 0.2 part of P-methoxyphenol were charged and reacted at 85 ° C. for about 10 hours, and when the isocyanate concentration reached 0.3%. The reaction was completed to obtain a urethane compound (A-1).

Application Example 1 15 parts of the urethane compound (A-1) obtained in Synthesis Example 1,
35 parts of pentaerythritol triacrylate, 30 parts of pentaerythritol tetraacrylate, 10 parts of trimethylolpropane triacrylate, 5 parts of 1,6-hexanediol diacrylate, 20 parts of tricyclodecane acrylate and 7 parts of 1-hydroxycyclohexyl phenyl ketone Then, the resin composition was dissolved to obtain a resin composition (optical disk material) of the present invention.

The above resin composition of the present invention was applied on a recording film of an optical disk having a recording film formed on a polycarbonate substrate by a spin coater, and irradiated with a high-pressure mercury lamp to cure the composition. 6 protectively coated optical disks
After performing a moist heat resistance test under the conditions of 0 ° C. and 90% RH,
There was no abnormality in the recording film or cured product even after 1000 hours. The surface resistance of the coated surface of the protective-coated optical disk was 1.1 × 10 12 Ω. Similarly, on the coated surface, a cigarette absorption test (the coated surface was rubbed fifteen times with a Teflon (registered trademark) cloth and then sprinkled with tobacco ash, and the non-adsorbed ash was wiped off the optical disc to remove the ash The degree of adhesion was visually observed.)
As a result, almost no ash adhesion was observed.

Application Example 2 Epoxy acrylate (Epicoat 828 (Bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.))
Was obtained by esterification with acrylic acid. 10 parts, 15 parts of the urethane compound (A-1) obtained in Synthesis Example 1, 40 parts of pentaerythritol triacrylate, 20 parts of tricyclodecane dimethylol diacrylate, 20 parts of tetrahydrofurfuryl acrylate and 1-hydroxycyclohexylphenyl 7 parts of ketone were mixed and dissolved to obtain a resin composition of the present invention (optical disc material). Using this, a protective-coated optical disk was obtained in the same manner as in Example 1. The test was performed in the same manner as in Example 1. As a result of the moist heat resistance test, there was no abnormality even after 1000 hours. The surface resistance was 9.5 × 10 11 Ω, and as a result of the tobacco adsorption test, almost no ash adhesion was observed.

Comparative Example 1 A resin composition (material for an optical disk) was obtained by mixing and dissolving in the same manner as in Example 1 except that the urethane compound (A-1) was omitted. Using this, a protective-coated optical disk was obtained in the same manner as in Example 1. The test was performed in the same manner as in Example 1. As a result of the moist heat resistance test, there was no abnormality even after 1000 hours. Surface resistance is 3.0 × 10
At 16Ω, the result of the tobacco adsorption test showed that ash had adhered.

[0039]

The cured product obtained by curing the resin composition using the urethane compound of the present invention has an antistatic property, hardly adheres dust, has good wet heat resistance, and is particularly suitable for optical disc protection. It can be suitably used as a coating agent and a hard coating agent for optical disks.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA13 AB14 AB20 AC01 AD01 BC13 BC34 BC81 BC87 4H006 AA01 AB46 4J011 AC04 QA03 QA06 QA07 QA08 QA14 QA18 QA33 QA38 QA39 QA40 QB01 QB05 QB13 QB14 QB15 QB14 QB14 SA16 SA21 SA22 SA31 SA32. LA06 LA07 LB07 LC13 LC25

Claims (5)

[Claims] 1. A urethane compound (A) which is a reaction product of a quaternary ammonium salt of bis (2-hydroxyethyl) taurine (a) and 2-isocyanatoethyl methacrylate (b). 2. A resin composition comprising the urethane compound (A) according to claim 1 and a compound (B) containing an unsaturated group other than the component (A). 3. The resin composition according to claim 2, which contains a photopolymerization initiator (C). 4. A material for an optical disk according to claim 2 or 3.
3. The resin composition according to item 1. 5. A cured product of the resin composition according to any one of claims 2 to 4.