JP2000273127A - Curable liquid resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which gives a cured material showing low surface resistance, shows good hardenability and enables high speed coating by forming the composition containing urethane (meth)acrylate, a reactive dilu ent, a polymerization initiator and a conductive powder having a diameter of not more than a specific value and/or an antistatic agent. SOLUTION: A composition of the present invention contains 5-90 pts.wt. of urethane (meth)acrylate, 5-90 pts.wt. of a reactive diluent, 0.1-10 pts.wt. of a polymerization initiator, 0.01-70 pts.wt. of a conductive powder having a diameter of not more than 0.3 μm such as antimony-doped tin oxide, or the like, and/or 0.01-45 pts.wt. of an antistatic agent such as a fatty acid ester of glycerol and the hardened material of the composition shows surface resistance of not more than 1×1012 Ω/(square). The urethane (meth)acrylate includes a reaction product of hydroxyethyl (meth)acrylate and 2,4-tolylene diisocyante. The reactive diluent to be used includes a polymerizable polyfunctional compound represented by the formula such as ethyleneglycol di(meth)acrylate, and the like (wherein R1 and R2 are each hydrogen or methyl; and (n) is 1-100).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrically conductive liquid curable resin composition which is used after being applied to the surface of glass, ceramics, plastic, wood or the like and cured.
More specifically, the present invention relates to a liquid curable resin composition which is excellent in coatability and curability, and is suitable as a coating material for optical fibers, optical fiber tape cores and the like.

[0002]

2. Description of the Related Art In the production of optical fibers, glass fibers are hot-melt spun and coated with a resin for protection and reinforcement. This process is called drawing, and as a resin coating, a structure is known in which a flexible primary coating layer is first provided on the surface of an optical fiber, and a rigid secondary coating layer is provided outside the primary coating layer. . Further, there is known a structure in which a plurality of these resin-coated optical fibers are arranged on a plane, hardened with a binding material, and provided with a tape-shaped coating layer. The resin composition for forming the primary coating layer is a soft material, the resin composition for forming the secondary coating layer is a hard material, and the resin composition for forming a tape-shaped coating layer. Is called a tape material.

[0003] The curable resin used as such a coating material for an optical fiber should have good coatability and be capable of drawing at high speed; have sufficient strength and flexibility; be excellent in heat resistance; Excellent; excellent resistance to acids, alkalis, etc .; excellent oil resistance; low water absorption and hygroscopicity; excellent weather resistance; low hydrogen gas generation: liquid and storage stability Characteristics such as good things are required.

In recent years, a large number of optical fibers have been used, and when connecting to equipment or apparatus, there has been a problem that the fibers are entangled by static electricity and the workability of the connection is deteriorated. In general, in order to suppress static electricity, it is conceivable to add antistatic ability to the material.Specifically, in order to increase the conductivity of the surface of the coating material and reduce the surface resistance, carbon powder is added to the resin or the resin is mixed. Attempts have been made to incorporate surfactants into these. However, carbon powder has a problem in that the transparency of the resin liquid or the cured product thereof is impaired. Therefore, there is a need for a resin composition for coating an optical fiber which has a cured product that is transparent and has a low surface resistance. Also, regarding the antistatic agent, in order to exhibit the antistatic effect, it is necessary to form a surfactant layer on the surface of the coating material, and a large amount of the surfactant is required, and the curability is impaired. there were. Therefore, there is a demand for a coating material in which the cured product exhibits low surface resistance, has good curability, and can be applied at high speed.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid curable resin composition which shows a low surface resistance of a cured product and is suitable for a transparent optical fiber coating material. Another object of the present invention is to provide a liquid curable resin composition suitable for an optical fiber coating material, in which the cured product exhibits low surface resistance, exhibits good curability, and can be applied at high speed. Further objects and advantages of the present invention will become apparent from the following description.

[0006]

According to the present invention, the above objects and advantages of the present invention include: (A) a urethane (meth) acrylate, (B) a reactive diluent, (C) a polymerization initiator, and (D) a polymerization initiator. This is achieved by a liquid curable resin composition containing a conductive powder having an average particle size of 0.3 μm or less and / or an antistatic agent.

The urethane (meth) acrylate as the component (A) of the present invention is produced by reacting a polyol, a diisocyanate and a hydroxyl group-containing (meth) acrylate. That is, it is produced by reacting an isocyanate group of a diisocyanate with a hydroxyl group of a polyol and a hydroxyl group of a (meth) acrylate containing a hydroxyl group, respectively.

The reaction may be, for example, a method in which a polyol, a diisocyanate and a hydroxyl group-containing (meth) acrylate are charged and reacted at once; a reaction between the polyol and the diisocyanate, followed by a hydroxyl group-containing (meth) acrylate.
A method of reacting an acrylate; a method of reacting a diisocyanate and a hydroxyl group-containing (meth) acrylate and then reacting a polyol; a method of reacting a diisocyanate and a hydroxyl group-containing (meth) acrylate, then reacting the polyol, and finally reacting the hydroxyl group-containing (meth) ) A method of reacting an acrylate.

The polyol preferably used herein includes, for example, polyether diol, polyester diol, polycarbonate diol, polycaprolactone diol and other diols. The polymerization mode of each structural unit of these diols is not particularly limited, and may be any of random polymerization, block polymerization, and graft polymerization. Examples of the polyether diol include polyethylene glycol, polypropylene glycol,
Examples thereof include polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and aliphatic polyether diols obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds. Examples of the ion-polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide,
3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate,
Butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether,
And cyclic ethers such as butyl glycidyl ether and glycidyl benzoate. Further, a polyether diol obtained by ring-opening copolymerization of the above ion-polymerizable cyclic compound with a cyclic imine such as ethyleneimine, a cyclic lactone acid such as β-propiolactone, glycolic acid lactide, or dimethylcyclopolysiloxanes. Can also be used. Specific combinations of the above two or more ion-polymerizable cyclic compounds include, for example, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1 And terpolymers of ethylene oxide, ethylene oxide, tetrahydrofuran, butene-1-oxide and ethylene oxide. The ring-opening copolymers of these ionic polymerizable cyclic compounds may be randomly bonded or may be in a block-like bond.

[0010] These aliphatic polyether diols
For example, PTMG650, PTMG1000, PTMG2
000 (Mitsubishi Chemical), PPG-400, PPG
1000, PPG2000, PPG3000, EXCE
NOL720, 1020, 2020 (all manufactured by Asahi Glass Urethane), PEG1000, Unisafe DC1100,
DC1800 (all manufactured by NOF Corporation), PPTG200
0, PPTG1000, PTG400, PTGL200
0 (from Hodogaya Chemical), Z-3001-4, Z-3
001-5, PBG2000A, PBG2000B (all manufactured by Daiichi Kogyo Seiyaku) and the like.

Further, as the polyether diol,
For example, alkylene oxide addition diol of bisphenol A, alkylene oxide addition diol of bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, alkylene oxide addition diol of hydrogenated bisphenol A, alkylene oxide addition diol of hydrogenated bisphenol F, alkylene hydroquinone Oxide addition diols, alkylene oxide addition diols of naphthohydroquinone, alkylene oxide addition diols of anthrahydroquinone, 1,4-cyclohexanediol and its alkylene oxide addition diols, tricyclodecanediol, tricyclodecanedimethanol, pentacyclopentadecanediol, penta Examples include cyclic polyether polyols such as cyclopentadecane dimethanol. It is. Of these, alkylene oxide-added diols of bisphenol A and tricyclodecane dimethanol are preferred. These polyols are, for example, Uniol DA400, DA700, DA1
000, DB400 (manufactured by NOF CORPORATION), and tricyclodecane dimethanol (manufactured by Mitsubishi Chemical) as commercial products. In addition, examples of the cyclic polyether diol include an alkylene oxide-added diol, an alkylenoxide-added diol of bisphenol F, and an alkylenoxide-added diol of 1,4-cyclohexanediol.

Examples of the polyester diol include a polyester diol obtained by reacting a dihydric alcohol with a dibasic acid. Examples of the dihydric alcohol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and
-Methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and the like. Examples of the dibasic acid include dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid. Commercially available products are Clapol P-2010, PMIP
A, PKA-A, PKA-A2, PNA-2000 (all made by Kuraray) and the like can be obtained.

Examples of the polycarbonate diol include polycarbonates of polytetrahydrofuran, polycarbonates of 1,6-hexanediol and the like, and commercially available products are DN-980, 981, 98 and 98.
2,983 (all made by Nippon Polyurethane), PC-80
00 (manufactured by U.S. PPG), PC-THF-CD (BASF
Manufactured).

Further, as the polycaprolactone diol, for example, ε-caprolactone and, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6- Polycaprolactone diol obtained by reacting with divalent diols such as hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,4-butanediol. These diols are available in Praxel 205, 205
It can be obtained as a commercial product such as AL, 212, 212AL, 220, 220AL (all manufactured by Daicel Chemical Industries, Ltd.).

Many other diols other than those described above can be used. Such other diols include, for example, ethylene glycol, propylene glycol, 1,4
-Butanediol, 1,5-pentanediol, 1,6-
Hexanediol, neopentyl glycol, 1,4-
Cyclohexane dimethanol, dimethylol compound of dicyclopentadiene, tricyclodecane dimethanol,
β-methyl-δ-valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, polydimethylsiloxane terminal diol compound, polydimethylsiloxane carbitol-modified diol, and the like.

In addition to using the diol as described above, it is also possible to use a diamine together with the diol. Examples of such a diamine include diamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4,4′-diaminodiphenylmethane, diamines containing a hetero atom, and polyether diamines.

Of these diols, polyether diols and bisphenol A alkylene oxide-added diols are preferred. For commercial products, PTMG650, PTM
G1000, PTMG2000 (Mitsubishi Chemical), Uniall DA400, DA700, DA1000, DB
400 (all manufactured by Nippon Oil & Fats).

As the diisocyanate, for example, 2,2
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate,
1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate,
4,4'-diphenylmethane diisocyanate, 3,3 '
-Dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4
-Trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate Isocyanate, 2,5 (or 2,6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane and the like can be mentioned. In particular, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate) and the like are preferable.

These diisocyanates can be used alone or in combination of two or more.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl ( (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate,
Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, the following formula (2) or (3)

[0021]

Embedded image

(Wherein, R ³ represents a hydrogen atom or a methyl group, and m represents a number of 1 to 15). Further, a compound obtained by an addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate and (meth) acrylic acid can also be used. Among these hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like are particularly preferable.

These hydroxyl group-containing (meth) acrylate compounds can be used alone or in combination of two or more.

The ratio of the polyol, diisocyanate and hydroxyl group-containing (meth) acrylate used is such that the isocyanate group contained in the diisocyanate is 1.1 to 3 equivalents per 1 equivalent of the hydroxyl group contained in the polyol, and the hydroxyl group of the hydroxyl group-containing (meth) acrylate is used. Is preferably 0.2 to 1.5 equivalents.

In the reaction of these compounds, for example, copper naphthenate, cobalt naphthenate, zinc naphthenate,
Dibutyltin dilaurate, triethylamine, 1,4-
A urethanization catalyst such as diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-diazabicyclo [2.2.2] octane is added in an amount of 0.2 to 100 parts by weight of the total reactants. It is preferable to use from 01 to 1 part by weight. The reaction is preferably carried out at a temperature of usually 10 to 90 ° C, particularly preferably 30 to 80 ° C.

A part of the hydroxyl group-containing (meth) acrylate can be replaced with a compound having a functional group which can be added to an isocyanate group. For example, γ-mercaptotrimethoxysilane, γ-aminotrimethoxysilane, and the like can be given. By using these compounds, the adhesion to a substrate such as glass can be increased.

The liquid curable resin composition of the present invention may further contain a urethane (meth) acrylate obtained by reacting 2 moles of a hydroxyl group-containing (meth) acrylate compound with 1 mole of diisocyanate. As such urethane (meth) acrylate, for example,
Reaction product of hydroxyethyl (meth) acrylate and 2,4-tolylene diisocyanate, hydroxyethyl (meth) acrylate and 2,5 (or 2,6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane The reaction product of hydroxyethyl (meth) acrylate and isophorone diisocyanate, the reaction product of hydroxypropyl (meth) acrylate and 2,4-tolylene diisocyanate, and the reaction product of hydroxypropyl (meth) acrylate and isophorone diisocyanate No.

The urethane (meth) acrylate comprising these polyols is preferably blended in the composition in an amount of 5 to 90 parts by weight, preferably 10 to 80 parts by weight.
It is more preferable that the compounding agent be added in an amount of not more than part by weight. If the amount is less than 5 parts by weight, the curability may be impaired. If the amount exceeds 90 parts by weight, the conductivity of the cured product may be impaired.

The reactive diluent as the component (B) includes
A polymerizable monofunctional compound or a polymerizable polyfunctional compound can be used. As such a monofunctional compound,
For example, alicyclics such as vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Formula structure-containing (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine and the like. Further, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate,
Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, methoxy polypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (Meth) acrylate, diethylaminoethyl (meth) acrylate, 7-
Amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-
Examples include dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and compounds represented by the following formulas (4) to (7).

[0030]

Embedded image

(Wherein R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ⁶ represents a hydrogen atom or 1 to 12 carbon atoms.
Preferably represents an alkyl group of 1 to 9, r is 0 to 12,
Preferably 1 to 8)

[0032]

Embedded image

(Wherein, R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group,
p is preferably a number from 1 to 4. )

[0034]

Embedded image

(Wherein R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently H or CH ₃ , and q is an integer of 1 to 5)

Among these polymerizable monofunctional compounds, vinyl-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate and lauryl acrylate are preferred.

Commercial products of these polymerizable monofunctional compounds include IBXA (manufactured by Osaka Organic Chemical Industry), Aronix M-
111, M-113, M114, M-117, TO-1
210 (all manufactured by Toagosei Co., Ltd.) can be used.

Examples of the polymerizable polyfunctional compound include, for example, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, triethylene glycol diacrylate, and tetraethylene glycol. Di (meth) acrylate, tricyclodecanediyldimethylenedi (meth) acrylate, 1,
4-butanediol di (meth) acrylate, 1,6-
Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bis-terminal diglycidyl ether adduct of (meth) acrylic acid ,
Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate,
Tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A ethylene oxide or propylene oxide adduct diol di (meth) acrylate, hydrogenated bisphenol A
Di (meth) acrylate of a diol of an adduct of ethylene oxide or propylene oxide, epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A, triethylene glycol divinyl ether, and the following formula (1) ^{_{CH 2 = C (R 1)}} -COO- (CH 2 -CH (R 2) -O) n -CO-C (R 1) = CH 2. . . (1) Here, R ¹ and R ² are each independently a hydrogen atom or a methyl group, and n is a number of 1 to 100.

Among these polymerizable polyfunctional compounds, compounds represented by the above formula (1), for example, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tricyclodecanediyl dimethylene di (meth) acrylate, ethylene Di (meth) acrylate of bisphenol A to which an oxide is added, and tris (2-hydroxyethyl) ioocyanurate tri (meth) acrylate are preferable.

Commercial products of these polymerizable polyfunctional compounds include, for example, Iupimer UV, SA1002 (manufactured by Mitsubishi Chemical), Aronix M-215, M-315, and M-32.
5 (all manufactured by Toagosei Co., Ltd.) can be used. Aronix TO-1210 (manufactured by Toagosei) can be used.

These reactive diluents are preferably blended in an amount of 5 to 90 parts by weight, more preferably 10 to 80 parts by weight, per 100 parts by weight of the composition. If the amount is less than 5 parts by weight, the curability may be impaired. If the amount exceeds 90 parts by weight, a change in the application shape due to low viscosity occurs, and the application is not stable.

Further, the liquid curable resin composition of the present invention contains a polymerization initiator as the component (C). As the polymerization initiator, a thermal polymerization initiator or a photoinitiator can be used.

When the liquid curable resin composition of the present invention is thermosetting, a thermal polymerization initiator such as a peroxide or an azo compound is usually used. Specific examples include benzoyl peroxide, t-butyl-oxybenzoate, azobisisobutyronitrile, and the like.

When the liquid curable resin composition of the present invention is photocurable, it is preferable to use a photopolymerization initiator and, if necessary, further use a photosensitizer. here,
Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, and 4-chloroacetate. Benzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone,
Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholino-
Propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-
Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; IRGACURE 184, 3
69, 651, 500, 907, CGI 1700, CG
I1750, CGI1850, CG24-61; Dar
Ocure 1116, 1173 (all manufactured by Ciba Specialty Chemicals); Lucirin TPO (B
ASF); Ubecryl P36 (UCB) and the like. Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine,
Ethanolamine, 4-dimethylaminobenzoic acid, 4-
Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate; Ubecryl P102, 103, 104, 105 (all manufactured by UCB) and the like.

When the liquid curable resin composition of the present invention is cured by using both heat and ultraviolet light, the above-mentioned thermal polymerization initiator and photopolymerization initiator can be used in combination. The polymerization initiator is used in an amount of 0.1 part by weight or more to 100 parts by weight of the above composition.
It is preferable that the compounding amount is 0 part by weight or less, particularly 0.5 part by weight or more and 7 parts by weight or less.

The liquid curable resin composition of the present invention further contains, as component (D), a conductive powder having a particle size of 0.3 μm or less and / or an antistatic agent. Examples of the conductive powder having an average particle size of 0.3 μm or less include tin oxide powder doped with antimony, tin oxide powder doped with phosphorus, indium oxide powder doped with tin, and zinc oxide. Powder, tin oxide powder, antimony oxide powder, carbon powder and the like. Of these, tin oxide powder or carbon powder doped with antimony and having an average particle size of 0.3 μm or less is preferable.

Antimony-doped average particle size of 0.3 μm
The average particle size of the tin oxide powder or carbon powder having a particle size of m or less is preferably 0.06 μm or less. If the average particle size exceeds 0.3 μm, the curability may be impaired or the drawability may be impaired. The conductive powder having an average particle size of 0.3 μm or less is preferably blended in an amount of 0.01 to 70 parts by weight, and more preferably 0.05 to 60 parts by weight. Is more preferred. Particularly preferably, it is 0.
1 part by weight or more and 55 parts by weight or less. If the amount is less than 0.01 part by weight, the conductivity tends to be impaired, and if it exceeds 70 parts by weight, the curability tends to be impaired. Such tin oxide powder doped with antimony can be obtained as a commercial product, for example, SN-1000P manufactured by Ishihara Sangyo Co., Ltd. The carbon powder can be obtained, for example, as Ketjen Black EC or Ketjen Black EC600JD manufactured by Lion Corporation.

As the antistatic agent, for example, polyoxyethylene alkylamine, glycerin fatty acid ester, quaternary ammonium salt, alkyl phosphate and the like can be used. These compounds can be used alone or in combination. The antistatic agent is composition 100
It is preferable that 0.01 to 45 parts by weight be blended in parts by weight, and particularly 0.1 to 40 parts by weight.
It is preferable that the compounding amount is not more than 0.2 parts by weight, particularly preferably not more than 0.2 parts by weight and not more than 35 parts by weight. If the amount is less than 0.01 part by weight, the antistatic ability is insufficient, and if it exceeds 40 parts by weight, the curability tends to be impaired. Such antistatic agents are commercially available, for example, Elegan 2 manufactured by NOF Corporation.
Available as 64-WAX.

The composition of the present invention may contain, if necessary, various additives such as an antioxidant, a colorant, an ultraviolet absorber, and the like, as long as the properties of the liquid curable resin composition of the present invention are not impaired.
Contains light stabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, solvents, fillers, anti-aging agents, wetting improvers, coating surface improvers, etc. can do.

The liquid curable resin composition of the present invention comprises:
Cured by heat and / or radiation. Here, radiation refers to infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α-rays, β-rays, γ-rays, and the like. The cured product of the liquid curable composition of the present invention preferably has a surface resistance of 1 × 10 ¹² Ω / □ or less, more preferably 1 × 10 ¹¹ Ω / □ or less, and particularly preferably 1 × 10 ⁸ Ω / □ or less. Indicates a value.

[0051]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Parts mean parts by weight unless otherwise specified.

Synthesis Example 1 (Synthesis of Urethane Acrylate) In a reaction vessel equipped with a stirrer, 13.48 parts of 2,4-tolylene diisocyanate, 0.015 part of 2,6-di-t-butyl-p-cresol, Dibutyltin dilaurate 0.05
And 0.0005 parts of phenothiazine, and the mixture was cooled with ice until the liquid temperature became 10 ° C. or lower while stirring.
After dropping 8.99 parts of 2-hydroxyethyl acrylate while controlling the liquid temperature to 20 ° C. or lower, the mixture was further reacted by stirring for 1 hour. Next, the number average molecular weight (G
Polystyrene equivalent number average molecular weight by the PC method; hereinafter the same)
46 parts were added, and stirring was continued at a liquid temperature of 60 to 70 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate became 0.1% by weight or less. The urethane acrylate resin liquid thus obtained is referred to as UA-1.

Synthesis Example 2 (Synthesis of Urethane Acrylate) In a reaction vessel equipped with a stirrer, 14.322 parts of 2,4-tolylene diisocyanate, 2,6-di-tert-butyl-p-
Cresol 0.014 parts, dibutyltin dilaurate 0.0
48 parts and 0.005 parts of phenothiazine were charged, and the mixture was cooled on ice with stirring until the liquid temperature became 10 ° C. or lower. Liquid temperature of 2-hydroxyethyl acrylate is 20
After dropping 11.147 parts while controlling the temperature to be lower than or equal to 0 ° C., the mixture was further reacted for 1 hour with stirring. Next, polytetramethylene glycol having a number average molecular weight of 2000 was added to 25.
332 parts, 8.639 parts of an alkylene oxide-added diol of bisphenol A having a number average molecular weight of 400 were added,
Stirring was continued at a liquid temperature of 60 to 70 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate became 0.1% by weight or less. The urethane acrylate resin liquid thus obtained is referred to as UA-2.

Example 1 In a reaction vessel equipped with a stirrer, 20.0 parts of UA-1 as the component (A) and 23.3 parts of tricyclodecanediyldimethyl (meth) acrylate as the component (B) of the present invention were placed. Part, N
10.0 parts of vinylcaprolactam, 6.7 parts of lauryl acrylate, Irgacure 18 as the component (C)
4 (Ciba Specialty Chemicals) to 3.0
0 parts and 40.0 parts of tin oxide powder SN-100P (manufactured by Ishihara Sangyo Co., Ltd.) doped with antimony as the component (D) were added and stirred until a uniform liquid was obtained to obtain the composition of the present invention.

Example 2 In a reaction vessel equipped with a stirrer, 20.0 parts of UA-1 as the component (A) and 20.0 parts of tricyclodecanediyldimethyl (meth) acrylate as the component (B) of the present invention were placed. Department,
10.0 parts of N-vinylcaprolactam, 5.0 parts of lauryl acrylate, Irgacure 1 as component (C)
Then, 3.00 parts of 84 and 45.0 parts of SN-100P as the component (D) were added, and the mixture was stirred until a uniform liquid was obtained to obtain a composition of the present invention.

Example 3 In a reaction vessel equipped with a stirrer, 20.0 parts of UA-1 as the component (A) and 20.0 parts of tricyclodecanediyldimethyl (meth) acrylate as the component (B) of the present invention were placed. Department,
10.0 parts of N-vinylcaprolactam, 5.0 parts of lauryl acrylate, Irgacure 1 as component (C)
84 and 3.0 parts of carbon black EC (manufactured by Lion) as a component (D) were added and stirred until a uniform liquid was obtained to obtain a composition of the present invention.

Comparative Example 1 In a reaction vessel equipped with a stirrer, 33.3 parts of UA-1 as the component (A) of the present invention and 38.8 parts of tricyclodecanediyldimethyl (meth) acrylate as the component (B) were added. Department,
16.7 parts of N-vinylcaprolactam, 11.2 parts of lauryl acrylate, Irgacure as component (C)
184 was added and stirred until a uniform liquid was obtained to obtain a composition.

Comparative Example 2 In a reaction vessel equipped with a stirrer, 20.0 parts of UA-1 as the component (A) of the present invention and 23.3 parts of tricyclodecanediyldimethyl (meth) acrylate as the component (B) were added. Part, N
10.0 parts of vinylcaprolactam, 6.7 parts of lauryl acrylate, Irgacure 18 as the component (C)
No. 4 was 3.00 parts, and instead of the component (D), 40.000 polyethylene glycol having a number average molecular weight of 400 was used as a surfactant.
0 parts were added and stirred until a uniform liquid was obtained to obtain a composition.

Example 4 In a reaction vessel equipped with a stirrer, 60 parts of the above-mentioned UA-2 as the component (A) of the present invention, 18 parts of tricyclodecanediyldimethyl (meth) acrylate as the component (B), N
-7 parts of vinylcaprolactam, 10 parts of polyethylene glycol diacrylate having a number average molecular weight of 400, 3 parts of Irgacure 184 as the component (C), and 5 parts of Elegan 264WAX (manufactured by NOF Corporation) as an antistatic agent of the component (D). The mixture was stirred at a liquid temperature of 50 ° C. until a uniform liquid was obtained to obtain a composition of the present invention.

Example 5 In a reaction vessel equipped with a stirrer, 60 parts of the above-mentioned UA-2 as the component (A) of the present invention, 12 parts of tricyclodecanediyldimethyl (meth) acrylate as the component (B), N
-8 parts of vinylcaprolactam, 15 parts of polyethylene glycol diacrylate having a number average molecular weight of 400, 3 parts of Irgacure 184 as the component (C), 5 parts of Elegan 264WAX as the component (D), and a liquid temperature of 50 ° C
Then, the mixture was stirred until a uniform liquid was obtained to obtain a composition of the present invention.

Example 6 In a reaction vessel equipped with a stirrer, 60 parts of the above-mentioned UA-2 as the component (A) of the present invention, 20 parts of tricyclodecanediyldimethyl (meth) acrylate as the component (B), N
5 parts of vinylcaprolactam, 12 parts of polyethylene glycol diacrylate having a number average molecular weight of 400, 3 parts of Irgacure 184 as the component (C), and 3 parts of Elegan 264WAX as the component (D), and a liquid temperature of 50 ° C.
Then, the mixture was stirred until a uniform liquid was obtained to obtain a composition of the present invention.

Comparative Example 3 Example 4 was repeated except that polyethylene glycol diacrylate having a number average molecular weight of 400 in the component (B) of Example 4 and Elegan 264WAX as the component (D) were not blended together.
And the same.

Comparative Example 4 The procedure of Example 4 was repeated except that the polyethylene glycol diacrylate having a number average molecular weight of 400 was not blended in the component (B), and that 3 parts of polyethylene glycol having a number average molecular weight of 400 was added instead of (D). Same as Example 4

Comparative Example 5 Comparative Example 4 was the same as Comparative Example 4, except that 20 parts of polyethylene glycol having a number average molecular weight of 400 were used.

Test Example 1 The liquid curable resin compositions shown in Examples 1 to 3 and Comparative Examples 1 and 2 were cured by the following method, and subjected to a surface resistance test, a curability test and a high-speed coating property test. went.

Preparation of Test Piece for Surface Resistance and Curability Test A liquid curable resin composition was applied on a glass plate using an applicator bar having a thickness of 60 μm, and 1 J / cm 2 in air using a conveyor type ultraviolet irradiation apparatus. Irradiation was performed with ultraviolet light having an energy of cm ² to obtain a cured film.

Surface Resistance Test RESISTIVITY CH manufactured by ADVANTEST
Using AMBER R1207A, the surface resistance of the cured film was measured as a one-minute value at an applied voltage of 100 V. A sample having a surface resistance of less than 1 × 10 ¹¹ Ω / □ was determined to be acceptable.

Curability Test The cured film was extracted with methyl ethyl ketone for 12 hours, and the weight retention was calculated by the following equation. Weight retention (%) = weight after extraction × 100 / weight before extraction A sample having a weight retention of 85% or more measured in this way was regarded as acceptable.

High-speed coating test A high-speed coating test was performed on melt-spun quartz glass under the following drawing conditions using an optical fiber drawing apparatus (manufactured by Yoshida Kogyo). The fiber diameter of the optical fiber was 150 μm in diameter, but a primary coating material described later was applied and cured to adjust the diameter to 200 μm, and further on the formed primary coating material, The compositions of Examples and Comparative Examples were applied and adjusted to 250 μm when cured, and applied. As the drawing speed of the optical fiber, a UV lamp made by ORC, SMX 3.5 kw was used as an ultraviolet irradiation device. The applicability was evaluated by setting the linear speed of the optical fiber to 600 m / m.
in, 800 m / min, 1000 m / min,
The wire diameter after application and curing at each speed was measured with a laser outer diameter measuring device manufactured by Anritsu Corporation, and a wire diameter variation within ± 1.0 μm was regarded as acceptable. The resin composition of the primary coating material of the optical fiber used in the drawing test was adjusted as follows.

Synthesis of Primary Coating Material In a reaction vessel equipped with a stirrer, 6.6 parts of 2,4-tolylene diisocyanate, 0.015 part of 2,6-di-t-butyl-p-cresol, 0 part of dibutyltin dilaurate .48 parts,
0.0005 parts of phenothiazine and 16.2 parts of IBXA (manufactured by Osaka Organic Chemical Industry) were charged, and the mixture was stirred and cooled with ice until the liquid temperature became 10 ° C. or lower. After dropping 2.9 parts of hydroxyethyl acrylate while controlling the liquid temperature to 20 ° C. or lower, the mixture was further stirred for 1 hour to react. Next, 50.0 parts of a number average molecular weight of 2,000 polytetramethylene glycol (manufactured by Mitsubishi Chemical) was added, and stirring was continued at a liquid temperature of 50 to 60 ° C. for 4 hours to reduce the residual isocyanate to 0.1% by weight or less. Time was defined as the end of the reaction. To this were added 10.8 parts of isobonyl acrylate, 4.8 parts of vinylcaprolactam and 5.10 parts of lauryl acrylate.
6 parts and 0.2 parts of Irganox 1035 were added, and the mixture was stirred at a liquid temperature of 40 to 50 ° C. for 30 minutes. Then 30-40
0.1 parts of diethylamine was added while controlling to
For 2 minutes, and while controlling the liquid temperature to 50 to 60 ° C., bis- (2,6-methoxybenzoyl) -2,4,4
-1 part of trimethylpentylphosphine oxide, Da
The mixture was stirred until a uniform transparent liquid was obtained. A primary coating material was obtained by this method. Table 1 shows the above test and evaluation results.

Test Example 2 The liquid curable resin compositions shown in Examples 4 to 6 and Comparative Examples 3 to 5 were cured by the following method, and the measurement of the surface resistivity and the weight retention was tested. Pass / fail evaluation was performed in the same manner as in Example 1. Table 2 shows the measurement results. Those having a surface specific resistance of less than 10 ¹² Ω / □ and a weight retention of 85% or more were judged as acceptable.

[0072]

[Table 1]

Comparative Examples 4 and 5 have high surface resistance and are outside the scope of the invention. Comparative Example 6 has a low weight retention and is out of the range of the invention.

As is clear from Table 1, the liquid cured resin composition of the present invention shows that the cured product has a low surface resistance, has good curability, and has excellent high-speed coating properties.
On the other hand, Comparative Example 1 shows high surface resistance, and Comparative Example 2 has poor curability and coatability.

[0075]

The liquid curable resin composition of the present invention shows a cured product having a low surface resistance, good curability, and is suitable for an optical fiber coating material which can be applied at high speed.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masanobu Sugimoto 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. Inside (72) Inventor Takashi Ukaji 2-11 Tsukiji 2-chome, Chuo-ku, Tokyo FSR (in reference) 2H050 BA13 BB07W BB14W BB17W BB19W BB31W 4J027 AC02 AC03 AC04 AC06 AF05 AG03 AG04 AG23 AG24 BA04 BA07 BA08 BA11 BA12 BA13 BA14 BA15 BA19 BA20 BA21 BA25 BA28 BA29 CA14 CA25 CB04 CB09 CB10 CC02 CC05 CD03 CD08 4J038 FA012 FA272 FA281 JB11 KA04 KA06 KA20 MA14 NA20 PC03 PC06

Claims (6)

[Claims] (A) urethane (meth) acrylate,
A liquid curable resin composition comprising (B) a reactive diluent, (C) a polymerization initiator, and (D) a conductive powder having an average particle size of 0.3 μm or less and / or an antistatic agent. 2. The reactive diluent (B) is represented by the following formula (1): CH ₂ ＣC (R ¹ ) —COO— (CH ₂ —CH (R ² ) —O) _n —CO—C (R ¹ ) = CH ₂ . . . (1) The liquid curable resin composition according to claim 1, wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, and n is a number of 1 to 100. 3. The liquid curable resin composition according to claim 1, wherein the conductive powder (D) is tin oxide powder or carbon powder doped with antimony and having an average particle size of 0.3 μm or less. 4. The liquid curable resin composition according to claim 1, wherein the antistatic agent (D) is a quaternary ammonium salt. 5. A cured product of the liquid curable resin composition according to claim 1. 6. The cured product according to claim 5, which has a surface resistance of 1 × 10 ¹² [Ω / □].