JPH09324136A - Liquid curable resin composition for covering optical fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a subject composition comprising a urethane (meth)acrylate, a polymerization initiator and polymer particles, excellent in the slipping property of the surface of a cured product, excellent in curability and durability and useful for air-blown fibers.

SOLUTION: This liquid curable resin composition comprises (A) a urethane (meth)acrylate, (B) a polymerization initiator and (C) polymer particles having an average particle diameter of 5μm to 1mm. The component A is obtained e.g. by reacting a polyol with a diisocyanate and an OH group-containing (meth) acrylate. The component B is e.g. a radical polymerization initiator and/or a radiation polymerization initiator, and the component C is e.g. acrylic resin particles. (D) A reaction diluent is preferably further added to the composition in an amount occupying the 20-70wt.% of the composition. The objective composition has a viscosity of 2000-15000cp at 25°C.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid curable resin composition for coating an optical fiber, which has excellent surface slipperiness after curing and excellent curability and durability.

[0002]

2. Description of the Related Art In the production of an optical fiber, a resin coating is applied for the purpose of protection and reinforcement immediately after hot-spinning a glass fiber. As this resin coating,
There is known a structure in which a flexible primary coating layer is first provided on the surface of an optical fiber, and a secondary coating layer having higher rigidity is provided outside the primary coating layer. In order to put these resin coated optical fiber wires into practical use, several
For example, it is known to make a so-called tape structure core wire in which four or eight pieces are arranged and covered with a binding material to form a tape-shaped structure having a rectangular cross section. Further, a method is also known in which two or more tape-structured core wires are further bundled to form multiple cores. For example, a 4-core tape-structured core wire is covered with two binding materials to form eight cores. There is. The resin composition used for these optical fiber coating applications is a resin material for forming the primary coating layer as a soft material, a resin composition for forming the secondary coating layer as a hard material, A binding material for bundling the strands to form a tape-structured core wire is called a tape material, and a binding material for further bundling the tape-structured core wire to form a multi-core is called a bundling material.
Furthermore, bundle several optical fiber strands into a cylindrical shape,
An air blown fiber is also known in which compressed air is used to fly inside a pipe that has been laid in advance, and the binding material for this purpose is called a binding material for air blown fiber. In recent years, as the density of optical fiber cables has been increased, a cable containing a large number of optical fiber tape structure core wires has been required. In addition, as the area where optical fibers are used expands, it has been desired to use air blown fibers for wiring farther.

[0003]

Such an optical fiber coating resin is generally liquid at room temperature and has high workability; quick curing and good productivity;
Sufficient strength and flexibility; little change in physical properties over a wide range of temperature changes; excellent heat resistance and hydrolysis resistance; little change in physical properties over time and excellent long-term reliability That it has excellent resistance to chemicals such as acids and alkalis; that it has low moisture absorption and water absorption; that it has excellent light resistance; that it has excellent oil resistance; that it produces hydrogen gas that adversely affects optical fibers. Characteristics such as small quantity are required.

Further, the optical fiber tape structure core wire used in the high density optical fiber cable is required to have a good slip property on the surface of the tape material or the bundling material. Also, as for the binding material for air blown fibers, it is desirable to use a material that has high slipperiness with the side wall of the pipe when flying in the pipe. Therefore, a tape material, a bundling material, and a bundling material for an air blown fiber, which are used for a high density optical fiber cable and an air blown fiber, need a material having a good surface property.

The object of the present invention is to satisfy the above-mentioned general required characteristics, and in particular, the surface after curing has a good slip property, and the curability is excellent, and the strength is sufficient. A liquid curable resin composition for optical fiber coating, which is suitable for use.

[0006]

The above objects and advantages of the present invention are (a) urethane (meth) acrylate and (b)
Polymerization initiator, and (c) average particle size of 5 μm or more and 1 m
It is achieved by a liquid curable resin composition for coating an optical fiber, which comprises polymer particles having a size of m or less. The present invention will be described in detail below, and other objects, advantages and effects of the present invention will be apparent.

(A) Urethane (meth) acrylate Urethane (meth) which is the component (a) used in the present invention
Acrylate can be produced by reacting a polyol, a diisocyanate and a hydroxyl group-containing (meth) acrylate. That is, it can be produced by reacting the isocyanate group of the diisocyanate with the hydroxyl group of the polyol and the hydroxyl group of the hydroxyl group-containing (meth) acrylate, respectively. As this reaction method, for example, a method in which a polyol, a diisocyanate and a hydroxyl group-containing (meth) acrylate are charged at once and reacted, a polyol and a diisocyanate are reacted, and then a hydroxyl group-containing (meth) acrylate is reacted; a diisocyanate and a hydroxyl group-containing ( Examples thereof include a method of reacting a (meth) acrylate and then a polyol; a method of reacting a diisocyanate and a hydroxyl group-containing (meth) acrylate, and then a polyol, and finally a hydroxyl group-containing (meth) acrylate.

Examples of the polyol used here include aliphatic, alicyclic or aromatic polyether diols, polyester diols, polycarbonate diols, polycaprolactone diols, etc. These polyols may be used alone or in combination of two or more. It can also be used. The polymerization mode of each structural unit in these polyols is not particularly limited, and random polymerization, block polymerization,
Any of graft polymerization may be used.

Of these, the aliphatic polyether diols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol and two or more ion-polymerizable cyclic compounds. And polyether diol obtained by ring-opening copolymerization.

Examples of the ion-polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane and trioxane. , Tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether,
Cyclic ethers such as allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and benzoic acid glycidyl ester are mentioned.

Specific examples of the polyether diol obtained by ring-opening copolymerization of two or more kinds of the ion-polymerizable cyclic compounds are, for example, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran. , A binary copolymer obtained by the combination of tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1-oxide and ethylene oxide; a terpolymer obtained by the combination of tetrahydrofuran, butene-1-oxide and ethylene oxide, and the like. be able to.

Further, ring-opening copolymerization of the above-mentioned ion-polymerizable cyclic compound and cyclic imine such as ethyleneimine; cyclic lactone acid such as β-propiolactone and glycolic acid lactide; or dimethylcyclopolysiloxane. It is also possible to use polyether diols.

The above-mentioned aliphatic polyether diol is, for example, PTMG650, PTMG1000, PTMG200.
0 (above, manufactured by Mitsubishi Chemical Corporation), PPG400, PPG
1000, EXCENOL 720, 1020, 2020
(Above, manufactured by Asahi Olin Co., Ltd.), PEG1000, Unisafe DC1100, DC1800 (above, manufactured by NOF Corporation), PPTG2000, PPTG1000, P
TG400, PTGL2000 (all made by Hodogaya Chemical Co., Ltd.), Z-3001-4, Z-3001-5, P
It can also be obtained as a commercial product such as BG2000A and PBG2000B (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

Examples of the alicyclic polyether diol include alkylene oxide addition diol of hydrogenated bisphenol A, alkylene oxide addition diol of hydrogenated bisphenol F, and alkylene oxide addition diol of 1,4-cyclohexanediol.

Examples of the aromatic polyether diol include alkylene oxide addition diol of bisphenol A, alkylene oxide addition diol of bisphenol F, alkylene oxide addition diol of hydroquinone, alkylene oxide addition diol of naphthohydroquinone, alkylene oxide addition diol of anthrahydroquinone. And so on. The aromatic polyether diol is, for example, Uniol DA400, DA70.
0, DA1000, DA4000 (above, NOF Corporation)
It is also available as a commercial product such as.

Examples of polyester diols include polyester polyols obtained by reacting a polyhydric alcohol with a polybasic acid. Examples of the polyhydric alcohol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol and 3- Methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and the like can be mentioned. Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid and the like. These polyester diols are Clapol P-201
0, PMIPA, PKA-A, PKA-A2, PNA-
2000 (above, manufactured by Kuraray Co., Ltd.) and the like are available as commercial products.

Examples of the polycarbonate diol include polytetrahydrofuran polycarbonate and 1,6-hexanediol polycarbonate. Commercially available products are DN-980, 981 and 98.
2,983 (all made by Nippon Polyurethane Co., Ltd.), PC
-8000 (manufactured by US PPG Corp.), PC-THF-C
D (manufactured by BASF) and the like.

Further, examples of the polycaprolactone diol include polycaprolactone diol obtained by reacting ε-caprolactone with a diol. Examples of the diol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol,
1,6-hexanediol, neopentyl glycol,
1,4-cyclohexanedimethanol, 1,4-butanediol and the like can be mentioned. These polycaprolactone diols are available as Praxel 205, 205AL, 212,
It can be obtained as a commercial product such as 212AL, 220, 220AL (all manufactured by Daicel Corporation).

Examples of polyols other than those mentioned above include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, Hydrogenated bisphenol A, hydrogenated bisphenol F, dimethylol compound of dicyclopentadiene, tricyclodecane dimethanol, pentacyclodecane dimethanol, β-methyl-δ-valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil Examples thereof include modified polyols, polydimethylsiloxane terminal diol compounds, and polydimethylsiloxane carbitol modified polyols.

The preferred molecular weight of the polyol used for producing the urethane (meth) acrylate is usually 50 to 15,000, preferably 100 to 8,000, in terms of polystyrene-equivalent number average molecular weight.

Examples of the diisocyanate used for producing the urethane (meth) acrylate include 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 '
-Dimethyl phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate) 2,2,4
-Trimethylhexamethylene diisocyanate, bis (2-isocyanate ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate Isocyanate and the like can be mentioned, particularly 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 used for producing urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2
-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, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate,
Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, the following formulas (1) and (2) CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ (OCOCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ). _n OH ・ ・ ・ (1) CH ₂ = C (R ¹ ) COOCH ₂ CH (OH) CH ₂ O (C ₆ H ₅ ) ・ ・ ・ (2) (In the formula, R ¹ represents a hydrogen atom or a methyl group. Shown, n is 1 to
(Which is an integer of 15). Also, alkyl glycidyl ether,
A compound obtained by an addition reaction of a glycidyl group-containing compound such as allyl glycidyl ether and glycidyl (meth) acrylate with (meth) acrylic acid can also be used.

Of these hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are particularly preferable.

These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more.

The use ratio of the polyol, diisocyanate and hydroxyl group-containing (meth) acrylate is such that the isocyanate group in the diisocyanate is 1.1 to 3 moles and the hydroxyl group in the hydroxyl group-containing (meth) acrylate is 1 mole of the hydroxyl group contained in the polyol. Is preferably 0.2 to 1.5 mol, and a ratio in which the total number of moles of hydroxyl groups contained in the polyol and the hydroxyl group-containing (meth) acrylate and the number of moles of isocyanate groups in the diisocyanate are substantially equal is particularly preferable.

When the urethane (meth) acrylate is produced, a compound having a functional group capable of being added to an isocyanate group may be used as an optional component. Examples of the above compound include γ-mercaptotrimethoxysilane and γ-aminotrimethoxysilane. By using these compounds, the adhesion of the resulting liquid curable resin composition to a substrate such as glass can be enhanced. These compounds can be used in an amount of preferably 10 parts by weight or less based on 100 parts by weight of all constituent components of urethane (meth) acrylate. When polyether diol is used as the polyol, diamine can be used together as an optional component. Examples of the diamine include ethylenediamine,
Examples thereof include tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4,4′-diaminodiphenylmethane and polyetherdiamine.

Furthermore, the composition of the present invention may further contain urethane (meth) acrylate obtained by reacting 1 mol of diisocyanate with 2 mol of a hydroxyl group-containing (meth) acrylate compound. Examples of the urethane (meth) acrylate include a reaction product of hydroxyethyl (meth) acrylate and 2,5 or 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, hydroxyethyl (meth) acrylate. And a reaction product of 2,4-tolylene diisocyanate, a reaction product of hydroxyethyl (meth) acrylate and isophorone diisocyanate, a reaction product of hydroxypropyl (meth) acrylate and 2,4-tolylene diisocyanate,
Examples include a reaction product of hydroxypropyl (meth) acrylate and isophorone diisocyanate. These urethane (meth) acrylates are preferably 3 when the total amount of urethane (meth) acrylate is 100 parts by weight.
It can be used in an amount of 0 parts by weight or less.

In the reaction for producing urethane (meth) acrylate from polyol, diisocyanate and hydroxyl group-containing (meth) acrylate, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, 1,1, A urethanization catalyst such as 4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-diazabicyclo [2.2.2] octane was added to 100 parts by weight of the total amount of the reactants. It is preferable to use 0.01 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.

Further, urethane (meth) acrylate is
The polystyrene reduced number average molecular weight is 500 to 20,0.
It is preferably 00. When the molecular weight is less than 500, the molecular weight between cross-linking points becomes small, so the flexibility of the cured product may be insufficient, and the shrinkage strain during curing may increase. If the molecular weight exceeds 20,000, the strength of the cured resin may be insufficient. Urethane (meth) acrylate is present in the composition of the present invention in an amount of 10
To 99% by weight, especially 20 to 99
% By weight is preferred.

(B) Polymerization Initiator The composition of the present invention is cured by heating and / or irradiation with radiation. Examples of the polymerization initiator which is the component (b) used in the present invention include a thermal polymerization initiator and a radiation polymerization initiator. Here, the radiation refers to infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like.

When the composition of the present invention is heat-cured,
Usually, radical polymerization initiators such as peroxides and azo compounds are used. As a specific radical polymerization initiator,
Examples thereof include benzoyl peroxide, t-butyl-oxybenzoate, azobisisobutyronitrile and the like.

When the composition of the present invention is cured by radiation, a radiation polymerization initiator is used. Here, as the radiation polymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 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-propane- 1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-
(2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like can be mentioned. As these commercial products, Irgacure1
84, 369, 651, 500, 907, CGI170
0, CGI1750, CGI1850, CG24-61
(The above is made by Ciba Geigy); Lucirin LR872
8 (manufactured by BASF); Darocure 1116, 117
3 (above, made by Merck); Yubecryl P36 (made by UCB)
And the like.

When the composition of the present invention is cured by heating and irradiation with radiation, the above-mentioned thermal polymerization initiator and radiation polymerization initiator may be used in combination. The polymerization initiator preferably accounts for 0.1 to 10% by weight, particularly 0.5 to 7% by weight, of the total composition.

(C) Polymer Particles Polymer particles used as the component (c) in the composition of the present invention include polyolefins, acrylic resins, polyurethanes, polyamides, polystyrenes, silicone resins, styrene / divinylbenzene copolymers, and the like. Particles may be mentioned. These polymer particles may be either crosslinked polymer particles or non-crosslinked polymer particles.
In particular, when cross-linked polymer particles are used, there is an advantage that the particles and the resin liquid are not compatible with each other and the shape of the polymer particles is hard to change. Moreover, as the polymer particles, particles of an acrylic resin such as polymethylmethacrylate are particularly preferable.
The acrylic resin is excellent in weather resistance because it does not contain an unsaturated bond in the polymer main chain, and at the same time, many crosslinkable monomers can be easily copolymerized at an arbitrary ratio, so that the polymer particles can be highly crosslinked.

Further, as the polymer particles, either one obtained by pulverizing a polymer into particles or polymerized into particles may be used. The shape of the particles may or may not be spherical. These polymer particles are, for example, Miperon XM-220 (manufactured by Mitsui Petrochemical Co., Ltd.), polymethylmethacrylate spherical fine particles MB, MBX, polystyrene particles SBX (above, manufactured by Sekisui Plastics Co., Ltd.), silicone highly functional powder trefil (Manufactured by Toray Dow Corning), true spherical functional fine particle polymer art pearl (manufactured by Negami Kogyo Co., Ltd.) and the like.

The specific gravity of the polymer particles is the resin composition obtained by removing the polymer particles from the composition of the present invention (hereinafter referred to as "resin liquid").
It is preferable that the specific gravity is the same as or close to that of
That is, the difference in specific gravity from the resin liquid is preferably 0.3 to -0.3. When the specific gravities of the resin liquid and the polymer particles are significantly different, sedimentation and floating of the polymer particles occur in a short time especially when the viscosity of the resin liquid decreases at high temperature, and the storage stability of the resin liquid in which the polymer particles are dispersed deteriorates. There are cases.
The average particle size of these polymer particles is 5 μm to 1 mm, and particularly preferably 10 μm to 500 μm. When the average particle diameter of the polymer particles is less than 5 μm, the surface slipperiness of the obtained cured product is insufficient, and when it exceeds 1 mm, the polymer particles become difficult to be stably dispersed in the resin liquid of the composition of the present invention. There is.

The polymer particles are added to the composition of the present invention in an amount of 0.1 from the viewpoint of imparting slipperiness to the surface of the cured product while maintaining the coatability with the viscosity of the composition of the present invention in an appropriate range.
-30% by weight is preferable, and more preferably 0.5-20% by weight.

Other Ingredients In addition to the above-mentioned ingredients, the composition of the present invention contains a reactive diluent, other oligomer, and a non-particulate polymer, if necessary, so long as the characteristics of the composition of the present invention are not impaired. , Other additives, etc. may be contained. The reactive diluent has a (meth) acryloyl group or a vinyl group,
A monomer other than the urethane (meth) acrylate as the component (a) is used. As such a monomer,
Examples include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, An alicyclic structure-containing (meth) acrylate such as cyclohexyl (meth) acrylate;

Benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, (meth) acryloylmorpholine, 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 (Meta)
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-dimethylaminopropyl (meth) acrylamide, the following formulas (3) to (5) CH ₂ = C (R ² ) COO (R ³ O) _m R ⁴ (3) [In the formula (3), R ² represents a hydrogen atom or a methyl group, and R ³
Represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, R ⁴ represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1
~ 9 alkyl groups, m is 0-12, preferably 1
~ Is an integer of 8]

[0043]

Embedded image

[In the formula (4), R ² is synonymous with the case of the formula (3), R ⁵ represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to ⁵ carbon atoms, and p is 1 to 8; It is preferably an integer of 1 to 4]

[0045]

Embedded image

[In the formula (5), R ² , R ⁵ and p are the same as those in the formula (4), and R ⁶ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms. (Meth) acryloyl group-containing monomer such as a compound represented by the formula: N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinylpyridine, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, N-vinyl. Mention may be made of vinyl group-containing monomers such as carbazole.

Commercially available products of these monofunctional monomers include, for example, Aronix M111, M113, M11.
4, M117 (above, Toa Gosei Kagaku); KAYARA
DTC110S, R629, R644 (above, manufactured by Nippon Kayaku); Viscoat 3700 (manufactured by Osaka Organic Chemical) and the like. Of these, isobornyl (meth) acrylate and N-vinylpyrrolidone are preferable.

Examples of polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di. (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-Hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate , Di (meth) acrylate of alkylene oxide addition diol of bisphenol A,
(Meth) acryloyl group-containing monomer such as hydrogenated bisphenol A alkylene oxide addition diol di (meth) acrylate and epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A; triethylene glycol di Examples thereof include vinyl group-containing monomers such as vinyl ether.

Commercially available products of these polyfunctional monomers are, for example, UPIMER UV, SA1002, SA2007.
(Made by Mitsubishi Yuka); Viscoat 700 (Osaka Organic Chemical); KAYARAD R-604, DPCA-2
0, -30, -60, -120, HX-620, D-3
10, D-330 (above, manufactured by Nippon Kayaku); Aronix M-210, M-215, M-315, M-325 (above, manufactured by Toagosei Kagaku). Among these, tricyclodecane dimethanol diacrylate and di (meth) acrylate of an alkylene oxide-added diol of bisphenol A are particularly preferred.

These reactive diluents can be used alone or in combination of two or more, and are usually blended so as to account for 80% by weight or less, preferably 20 to 70% by weight in the composition of the present invention. Preferably. When the amount ratio of the reaction diluent is within the above range, the coatability and the curing rate are appropriately maintained, the toughness of the cured product is appropriate, and the curing shrinkage rate is low.

Other oligomers include, for example, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, siloxane having a (meth) acryloyloxy group, fluorine-based oligomer, silicone-based oligomer, polysulfide-based oligomer, etc. Can be mentioned. Further, as the non-particulate polymer, for example, a reactive polymer obtained by reacting a copolymer of glycidyl (meth) acrylate and other vinyl group-containing monomer with acrylic acid, polyamide, polyamideimide, polyurethane, polybutadiene, Polyether, polyester, pentadiene derivative, styrene-butadiene-styrene block copolymer, styrene-ethylene-butene-styrene block copolymer, styrene-isoprene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, etc. Can be mentioned.

Further, the composition of the present invention may contain an amine in order to suppress generation of hydrogen gas which causes transmission loss of the optical fiber. Examples of such amines include diallylamine, diisopropylamine, diethylamine, diethylhexylamine and the like. Further, in addition to the above components, various additives such as antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, colorings. An agent, a solvent, a filler, an antiaging agent, a wettability improving agent, a coating surface improving agent and the like can be added as necessary.

Here, examples of the antioxidant include Ir
ganox 1010, 1035, 1076, 1222
(Above, made by Ciba Geigy), Antigen P, 3
C, FR, GA-80 (made by Sumitomo Chemical), etc. are mentioned. As the ultraviolet absorber, for example, Tinuvin
P, 234, 320, 326, 327, 328, 32
9, 213 (all made by Ciba Geigy), Seesorb
102, 103, 501, 202, 712, 704 (above, manufactured by Cypro Kasei) and the like. As the light stabilizer, for example, Tinuvin 292, 144, 622L
D (above, manufactured by Ciba Geigy), Sanol LS770 (manufactured by Sankyo), and Sumisorb TM-061 (manufactured by Sumitomo Chemical). Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ
-Mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and commercially available products include SH6062, 6030 (above, manufactured by Toray Silicone), KBE903, 603, 403 (above, manufactured by Shin-Etsu Chemical). The viscosity of the composition of the present invention is 25
The value measured at 0 ° C is usually preferably 200 to 20000 cp, and particularly preferably 2000 to 15000 cp.

[0054]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 In a reaction vessel equipped with a stirrer, 1127 g of tricyclodecane dimethanol diacrylate, 1453 g of 2,4-tolylene diisocyanate, 4.5 g of dibutyltin dilaurate and 2,6-di-t-butyl- as a polymerization inhibitor. Four
-1.5 g of methylphenol and 0.5 of phenothiazine
I charged g. After cooling this to 10 ° C in an ice water bath,
1266 g of hydroxyethyl acrylate at a temperature of 2
It was added while controlling at 0 ° C or lower. 10 more after addition
After stirring at -20 ° C for 1 hour, 704 g of polyoxyethylene bisphenol-A ether and number average molecular weight of 2
2,000 polytetramethylene glycol 2250g
Was added while keeping the temperature below 50 ° C. Then
After stirring at 50-60 ° C for 5 hours, the reaction was terminated.
In this way, urethane acrylate (83% by weight)
And 6806.5 g of a mixture of tricyclodecane dimethanol diacrylate (17% by weight) as a reactive diluent was obtained. Further, 493 g of a reaction diluent tricyclodecane dimethanol diacrylate, 773 g of isobornyl acrylate, 700 g of ethylene oxide adduct diol diacrylate of bisphenol A, 895 g of N-vinylpyrrolidone, and 290 g of a photopolymerization initiator Irgacure 184 (manufactured by Ciba Geigy) were further added. In addition, the mixture was stirred at 45 to 55 ° C. for 3 hours, and at 20 ° C. to 30 ° C., Art Pearl G-400 (average particle diameter 15 μm; manufactured by Negami Kogyo Co., Ltd.), which is a crosslinkable polymethylmethacrylate particle as polymer particles, 5
The composition of the present invention 1 was prepared by adding 00 g and stirring for 1 hour.
0457.5 g was obtained.

Example 2 As polymer particles, Art Pearl G-200 (average particle diameter 30 μm) which is a crosslinkable polymethylmethacrylate particle was used.
m; manufactured by Negami Kogyo Co., Ltd.) was used to obtain a composition of the present invention in the same manner as in Example 1. Example 3 A composition of the present invention was obtained in the same manner as in Example 1 except that polyurethane particles, Art Pearl C-400 (average particle size 15 μm; manufactured by Negami Kogyo Co., Ltd.) were used as the polymer particles. Example 4 A composition of the present invention was obtained in the same manner as in Example 1, except that polyurethane particles Art Pearl C-200 (average particle size 30 μm; manufactured by Negami Kogyo Co., Ltd.) were used as the polymer particles.

COMPARATIVE EXAMPLE A composition was obtained by repeating the example except that no polymer particles were incorporated.

Test Example The viscosities of the compositions obtained in Examples 1 and 2 and Comparative Example were measured according to the following evaluation methods, and the slipperiness of the surface of the cured product and the strength of the cured product were evaluated. The results are shown in Table 1. (Measurement of viscosity) Using a B-type viscometer manufactured by Tokyo Keiki, 25 ° C
It was measured at. (Evaluation of slipperiness of cured product surface) 1. Preparation of test piece The composition was applied on a glass plate using an applicator bar having a thickness of 75 μm, and this was applied under a nitrogen atmosphere at 100 mJ / cm 2.
A cured film having a film thickness of 50 μm was obtained by irradiating the ultraviolet ray of ² . Next, the cured film was peeled off from the glass plate, and left for 24 hours in an atmosphere of 23 ° C. and a relative humidity of 50% was used as a test piece. 2. Shear-slip test A pair of test pieces were attached to an aluminum plate with double-sided tape, and a pair was made so that the surface portion of the film was in contact with each other and fixed with a stack clip. The pressure applied to the contact surface of the test piece when it was fixed with the clip was 0.241 kg / mm ² . The two aluminum plates were pulled by using a gripping tool (pulling speed 50 mm / min), and the stress required for the sample to start sliding was measured. (Evaluation of Strength of Cured Product) 1. Preparation of test piece The composition was applied onto a glass plate using an applicator bar having a thickness of 150 μm, and this was applied under an air atmosphere to 1.0 J / cm ^2.
By irradiating with the ultraviolet ray of No. 1, a cured film having a film thickness of 120 μm was obtained. Next, the cured film was peeled off from the glass plate, and left for 24 hours in an atmosphere of 23 ° C. and a relative humidity of 50% was used as a test piece. 2. Measurement of tensile elastic modulus A test piece is cut into a strip with a width of 6 mm, and JIS K7113 is used.
The tensile modulus at 23 ° C. was measured in accordance with However, the tensile speed was 1 mm / min, and the tensile modulus was calculated from the tensile stress at a strain of 2.5%.

[0058]

[Table 1]

[0059]

Since the liquid curable resin composition for coating an optical fiber of the present invention has a good surface slipperiness after curing, a tape material, a bundling material and a tape material used for a high-density fiber cable or air blown fiber and It is especially useful as a binding material for air blown fibers

The present invention described in detail above will be described below, including preferred embodiments. 1. A liquid curable resin for coating an optical fiber, comprising (a) a urethane (meth) acrylate, (b) a polymerization initiator, and (c) a polymer particle having an average particle size of 5 μm or more and 1 mm or less. Composition. 2. The composition according to the above 1, wherein the urethane (meth) acrylate (a) is obtained by reacting a polyol, a diisocyanate and a hydroxyl group-containing (meth) acrylate. 3. The composition according to the above 1, wherein the reactive diluent accounts for 20 to 70% by weight of the composition. 4. The composition according to 1 above, wherein the polymerization initiator is a radical polymerization initiator and / or a radiation initiator. 5. The above 1 in which the polymer particles are acrylic resin particles
A composition according to claim 1. 6. The composition has a viscosity of 2,000 to 15, measured at 25 ° C.
The composition according to 1 above which is 000 cp.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Takeshi Hirai, 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd. (72) Takashi Ukaji 2--1124 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] (1) urethane (meth) acrylate,
A liquid curable resin composition for optical fiber coating, comprising (b) a polymerization initiator, and (c) a polymer particle having an average particle diameter of 5 μm or more and 1 mm or less.