JP2001199748A - Resin composition for covering optical fiber and covered core wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actinic energy curable resin composition to be applied to an optical fiber as a primary coating, secondary coating, color layer, unit material or overcoat, durable to the recently required high-speed processing, having high curability sufficiently curable with low irradiation dose, satisfying mechanical characteristics necessary for core wire, colored core wire, core wire unit and overcoated core wire and having excellent toughness and provide a product produced by using the composition. SOLUTION: The objective resin composition for the coating of an optical fiber contains (A) an asymmetric polymerizable linear polyurethane compound having >=2 radical-polymerizable groups on one terminal and one radical- polymerizable group on the other terminal and producible by using a diol compound, a diisocyanate compound, a compound having one hydroxy group and >=2 radical-polymerizable groups and a compound having one hydroxy group and one radical-polymerizable group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for coating an optical fiber which significantly improves productivity in the production of an optical fiber, a colored optical fiber, an optical fiber unit and the like, and an optical fiber core, a coated core, a unit or This is for the overcoat core wire.

[0002]

2. Description of the Related Art In recent years, optical fibers have made dramatic technological progress as transmission media for large-capacity information, and have been developed in various fields.
It's being used.

Usually, an optical fiber has an outer diameter of about 125 μm.
, In which information is transmitted through light. However, glass is susceptible to physical damage due to contact with other objects or dust in the atmosphere, and chemical erosion due to chemical substances such as moisture in the air. There is a disadvantage of breaking. Furthermore,
The optical fiber has a drawback that, when stress is applied from the outside, the loss of light passing through the glass becomes large and information cannot be transmitted accurately.

In order to solve these drawbacks, an optical fiber is usually provided with a resin coating layer comprising an extremely flexible primary coating layer and a highly rigid secondary coating layer. As the resin for resin coating, it is necessary to form a resin coating layer at the same time as melting and drawing a glass rod at a high temperature. A line-curable resin composition is used.

An optical fiber provided with a resin coating layer comprising the above-mentioned primary coating layer and a highly rigid secondary coating layer.
The form of a colored optical fiber having a colored layer having a thickness of several to several tens μm on the (core wire) for identification (colored core wire), and an optical fiber unit (unit) in which a plurality of colored core wires are assembled and integrated. (Including a tape unit in which the cords are gathered in a tape shape in parallel), several tens to
There is also a form in which an overcoat layer having a thickness of several hundred μm is provided (overcoat core wire), and an active energy ray-curable resin composition is used as the coloring layer, the unit material, and the overcoat layer. .

[0006] These active energy ray-curable resin compositions are required to have the following performance. (High-speed processability): Liquid, excellent workability when coating optical fiber. (Storage stability): Viscosity does not change when stored at low or high temperature, and excellent long-term stability. (Curability): High curing speed and high processing speed. (Toughness): The cured product has sufficient tensile fracture elasticity and tensile fracture elongation. (Hereinafter referred to as a coated core) has sufficient mechanical strength. (Temperature dependency): The cured product has a small change in physical properties due to a wide range of temperature changes, and the temperature change of the optical signal transmission characteristics of the coated core. (Environmental resistance): The cured product has heat resistance, hydrolysis resistance, acid resistance, alkali resistance, oil resistance, light yellowing resistance, heat yellowing resistance,
For example, the UV resistance is excellent, and the coated core wire has excellent environmental resistance. Among them, a resin composition for coating an optical fiber having a high curing rate (high curability) is particularly desired in order to enhance mass productivity due to an increasing demand for an optical fiber.

In order to satisfy the above-mentioned required properties, various ultraviolet curable compositions for coating optical fibers have already been proposed. For example, (a) a bifunctional (diethylenic) polymerizable polyurethane based on diisocyanate (JP-A-59
-170155), (b) a tetrafunctional polymerizable polyurethane obtained by reacting a polyhydroxy-functional amine having an amino hydrogen atom (Japanese Patent Application Laid-Open No. 62-12640), and (c) a trifunctional or higher functional core-based multifunctional. Polymerizable polyurethanes (JP-A-62-21734, JP-A-62-10691)
8), (d) a tetrafunctional polymerizable polyurethane obtained by reacting a diacrylate of trishydroxyalkyl isocyanurate (JP-A-61-227947), and (e) an isocyanuric acid derivative having a polymerizable unsaturated group and a hydroxyl group at the terminal. And trifunctional polymerizable polyurethanes (JP-A-5-271719) obtained by the reaction of a polyisocyanate with a compound having a polymerizable unsaturated group and a hydroxyl group at the terminal.

However, optical fiber coating compositions using these polymerizable polyurethane compounds have the following problems in practical use. That is, the resin composition using the diethylenically polymerizable polyurethane (a) having a functional number of 2 has a low curing rate and cannot reach the curability required at present. Also, the functional number is 3 or more (b),
When the polymerizable polyurethanes of (c), (d), and (e) are used, the curability is superior to that of (a), but when used for a cored wire, the toughness is poor, and the proof at the time of optical fiber production is poor. The test breaks the glass and the coating. Also,
Also when used as a unit material, an overcoat material, etc., there was a disadvantage that the toughness was insufficient, so that it was easily broken in a mechanical property test. In addition, the curability was not sufficiently satisfactory.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an optical fiber coating composition having high curability, excellent toughness and excellent storage stability.

[0010]

Means for Solving the Problems In view of this situation, the present inventors have conducted intensive studies to solve the above problems, and as a result,
When an asymmetric polymerizable linear polyurethane compound (A) having two or more radically polymerizable groups at one end and one radically polymerizable group at the other end is used, the curability is high, the toughness is excellent, and It has been found that a resin composition for coating an optical fiber having excellent storage stability can be provided.

That is, the present invention including a configuration for solving the above-mentioned problem is as described in each claim of the claims and is as follows.

(Claim 1) An asymmetric polymerizable linear polyurethane compound (A) having two or more radically polymerizable groups at one end and one radically polymerizable group at the other end. Optical fiber coating resin composition.

(Claim 2) The asymmetrically polymerizable linear polyurethane compound (A) has two or three radically polymerizable groups at one end and one radically polymerizable group at the other end. The resin composition according to claim 1, which is a linear polyurethane compound.

(Claim 3) The resin composition according to claim 1 or 2, wherein the asymmetric polymerizable linear polyurethane (A) is a polyetherdiol polyurethane.

(4) The resin composition according to any one of (1) to (3), wherein the asymmetric polymerizable linear polyurethane (A) is a polyether diol polyurethane having a side chain.

(Claim 5) The asymmetric polymerizable linear polyurethane compound (A) has a number average molecular weight of 500 to 20,000.
The resin composition according to claim 1, 2, 3, or 4, wherein

(Claim 6) When the tensile modulus of the cured product of the resin composition is 0.05 to 1 kg / mm ² , the asymmetrically polymerizable linear polymer having a number average molecular weight of 3,500 to 20,000. The polyurethane compound (A) was added to 35 to 9 based on 100 parts of the sum of (A) and the other polymerizable unsaturated compound (B).
5 parts, the tensile modulus of the cured product of the resin composition was 1 to 200
When the weight average molecular weight is 500-kg / mm ² ,
The asymmetric polymerizable linear polyurethane compound (A) of 3,500 is replaced with (A) and another polymerizable unsaturated compound (B).
The resin composition according to any one of claims 1 to 5, wherein the resin composition contains 20 to 80 parts with respect to 100 parts of the total.

(7) An optical fiber core, a colored core, a unit or an overcoat core coated with a cured product of the resin composition according to any one of (1) to (6).

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION An asymmetric polymerizable linear polymer having two or more radically polymerizable groups at one end and one radically polymerizable group at the other end, which is a component constituting the resin composition of the present invention. The polyurethane compound (A) is a diol compound (A-
1) a diisocyanate compound (A-2) and a monohydric group-containing compound (A-3) having two or more radically polymerizable groups
And a monohydroxyl-containing compound (A-4) having one radical polymerizable group. Diol compound (A-1)
Examples thereof include alkylene diol (A-1-1), polyether diol (A-1-2), polyester diol (A-1-3), and polycarbonate diol (A-1-
4) and so on.

Examples of the alkylene diol (A-1-1) include C ₂ -C ₂₀ diols;
Propylene glycol, 1,4-butanediol, 1,
5-pentanediol, neopentyl glycol, 1,
6-hexanediol, 1,9-nonanediol, 1,
10-decanediol, higher fatty acid polyols and higher hydrocarbon polyols {e.g. castor oil, coconut oil, monomyristine, monopalmitin, monmostearin, monoolein, 9,10-dioxystearic acid, 12-hydroxystearyl alcohol, 16-hexadecanediol, 1,21-hemicosandiol, chimyl alcohol, batyl alcohol, seralkyl alcohol, dimer acid diol, etc., hydrogenated dimer diol, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, hydroxy-terminated polyisoprene And hydrogenated polyisoprene, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, a dimethylol compound of dicyclopentadiene, and tricyclodecanedimethanol. When it is necessary to maintain a high tensile fracture modulus at high temperature, a diol having a ring structure is effectively used. Preferred diols having a ring structure include hydrogenated bisphenol A, hydrogenated bisphenol F, and tricyclodecane dimethanol. As a commercial product,
Tricyclodecane dimethanol (Mitsubishi Chemical Corporation)
Etc.

The polyether diol (A-1-2) includes a ring-opened polymer of one or more cyclic ethers of C _{2 to} C ₁₀ . Polyether polyols obtained by homopolymerization include polyethylene glycol and polypropylene glycol, and commercially available products (trade names, the same applies hereinafter) include Takelac P-22, Takelac P-22, Takelac P-
23 (manufactured by Takeda Pharmaceutical Co., Ltd.), polytetramethylene glycol, commercially available as PolyTHF250, Poly
THF650, PolyTHF1000, PolyTHF
2000, PolyTHF2900, PolyTHF45
00 (above, manufactured by BASF, Germany), polyoxybutene-1 oxide, PBG1000, PBG
3000 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), such as polyhexamethylene glycol, polyheptamethylene glycol, and polydecamethylene glycol.

In the polyether diol obtained by ring-opening copolymerization, cyclic ethers include, for example, ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 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, butyl glycidyl ether, glybenzoic acid There are cyclic ethers such as succinimidyl ester. Further, a polyether diol obtained by ring-opening copolymerization of the above cyclic ether with a cyclic imine such as ethyleneimine, a cyclic lactonic acid such as β-propiolactone or glycolic lactide, or a dimethylcyclopolysiloxane is used. May be.

Specific combinations of the above two or more cyclic compounds include, for example, tetrahydrofuran and ethylene oxide, commercially available products such as Unisafe DC1100,
Unisafe DC1800 (Nippon Oil & Fats Co., Ltd.), tetrahydrofuran and propylene oxide, commercially available as Unisafe DCB1800 and Unisafe DCB11
00 (above, NOF Corporation), PPTG1000, P
PTG2000, PPTG4000 (both manufactured by Hodogaya Chemical Co., Ltd.), tetrahydrofuran and 2-methyltetrahydrofuran or 3-methyltetrahydrofuran, PTG-L1000, PTG-L200 as commercial products
0, PTG-L3000 (above, Hodogaya Chemical Co., Ltd.)
Propylene oxide and ethylene oxide, butene-1-oxide and ethylene oxide, butene-1-oxide and propylene oxide binary copolymer, tetrahydrofuran and butene-1-oxide and ethylene oxide, tetrahydrofuran And a terpolymer of butene-1-oxide and propylene oxide. These ring-opening copolymers may be bonded at random or may be bonded in a block shape.

In a polyether diol obtained by ring-opening polymerization of a cyclic ether to a dihydroxy group-containing compound, examples of the dihydroxy group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 6 hexanediol, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F and the like. As the cyclic ether, those described above are used. Examples are ethylene oxide adducts of bisphenol A, and commercially available products, Uniol DA-400 and Uniol DA-700.
(Manufactured by NOF Corporation), a propylene oxide adduct of bisphenol A, Uniol DB-400 as a commercial product
Etc.

A cured product of a resin composition using a homopolymer or a copolymer of tetrahydrofuran is characterized by a small change in physical properties due to a wide range of temperature change. The resin composition using the polypropylene glycol does not crystallize at a low temperature, has a low viscosity, and has good workability.

Examples of the polyester diol (A-1-3) include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, butanediol, polybutanediol, neopentyl glycol, 6-hexanediol, 3-
Methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,
Dihydric alcohols such as 4-cyclohexanedimethanol, dimethanolated dicyclopentadiene, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, polydimethylsiloxane-terminated diol, and polydimethylsiloxane carbitol-modified polyol Diols obtained by reacting carboxylic acids with polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, dimer acid, and the like. , PKA-A, PKA-A
2, PNA-2000 (made by Kuraray Co., Ltd.) and the like,
There is a polylactone diol obtained by reacting the above dihydric alcohols with lactones such as ε-caprolactone and β-methyl-δ-valerolactone. As polylactone diol, polycaprolactone diol, and as commercial products, Praxel 205, 205AL, 212, 212
AL, 220, 220AL (all manufactured by Daicel Corporation)
There is.

The resin composition using the polyester diol has low moisture absorption and excellent heat resistance as compared with the polyether diol. However, it has a disadvantage of high viscosity and poor hydrolysis resistance, and it is necessary to select a polymerizable unsaturated compound and adjust the viscosity and the water absorption to a low level.

Polycarbonate diol (A-1-4)
As a C ₂ -C ₁₀ alkylene carbonate. For example, there are polycarbonates of polytetrahydrofuran, polycarbonates of 1,6-hexanediol, and the like. Commercial products include DN-980, 981, 982,
983 (all made by Nippon Polyurethane Co., Ltd.), PC-8
000 (manufactured by PPG, USA), PC-THF-CD
(Manufactured by BASF).

A urea group may be introduced by replacing part or all of the diol compound (A-1) with a diamine compound. As the diamine compound, for example, ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4,
There are 4'-diaminophenylmethane, polyoxypropylenediamine, polyoxytetramethylenediamine and the like.

As the diol compound (A-1), alkylene diol, polyether diol, polyester diol and polycarbonate diol are preferred. Polyether polyol (A-1-2) which has low viscosity, good high-speed processability, and provides curability and toughness is preferred. In particular, tetrahydrofuran, propylene oxide, butene-1-
Homopolymers or cyclic copolymers of cyclic ethers such as oxide, isobutene oxide, 2-methyltetrahydrofuran and 3-methyltetrahydrofuran are preferred. One or a combination of two or more may be used.

In particular, when a polyether polyol having a side chain (a main chain having a substituent having one or more carbon atoms is referred to as a side chain) is used, there is no crystallization at a low temperature, and An asymmetric polymerizable linear polyurethane compound (A) having excellent viscosity, curability and toughness is obtained. Examples of the polyether polyol having a side chain include a homopolymer of a cyclic ether having a substituent such as propylene oxide, butene-1-oxide, isobutene oxide, 2-methyltetrahydrofuran, and 3-methyltetrahydrofuran, or a cyclic ether having this substituent. It is a copolymer of cyclic ether containing ether as an essential component. One or a combination of two or more may be used.

Examples of the diisocyanate compound (A-2) include trimethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate,
2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,4
-Cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane 1,3-bis (isocyanatomethyl) cyclohexane, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,
4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, dianidin diisocyanate, , 4'-diphenyl ether diisocyanate, 1,3- or 1,4-xylylene diisocyanate, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene, m -Xylene diisocyanate, lysine diisocyanate methyl ester, isophorone diisocyanate,
3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-phenylene diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, 2,5
-Bis (isocyanatomethyl) -bicyclo [2.2.
1] heptane, 2,6-bis (isocyanatomethyl)
-Bicyclo [2.2.1] heptane, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,
Examples include 3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated xylylene diisocyanate, tolidine diisocyanate, transcyclohexane 1,4-diisocyanate, tetramethyl xylene diisocyanate, hydrogenated dimer diisocyanate, norbornene diisocyanate, and the like.

The hydroxyl-containing compound (A-2-2) having no radically polymerizable group is reacted with the isocyanate compound (A-2-1) having three or more isocyanate groups,
A compound having a small number of isocyanate groups and having two isocyanate groups may be used.

Examples of the isocyanate compound (A-2-1) having three or more isocyanate groups include triphenylmethane triisocyanate, tris (4-phenyl isocyanate) thiophosphate, and 2,4-tolylene diisocyanate trimethylolpropane adduct. Isomer, hexamethylene diisocyanate-trimethylolpropane adduct, 2,4-tolylene diisocyanate dimer, hexamethylene diisocyanate trimer, 2,4-
Tolylene diisocyanate trimer, 2,4-tolylene diisocyanate (3 mol) -hexamethylene diisocyanate (2 mol) copolymer, hexamethylene diisocyanate (3 mol) -water (1 mol) copolymer lysine triisocyanate There is. Examples of the hydroxyl group-containing compound (A-2-2) having no radical polymerizable group include methanol,
Examples include ethanol, isopropyl alcohol, n-butyl alcohol, iso-butyl alcohol, t-butyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, and tetrahydrofurfuryl alcohol.

Among these diisocyanate compounds,
Preferred are 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate) and the like. One or a combination of two or more may be used.

The monohydroxyl-containing compound (A-3) having two or more radically polymerizable groups will be described. In the monohydric group-containing compound (A-3) having two or more radically polymerizable groups, the radically polymerizable group includes a (meth) acryl group,
There are (meth) allyl group, vinyl group, (meth) acrylamide group and the like. (Meth) acrylic group, vinyl group, (meth)
Acrylamide groups are preferred because of their high reactivity.

The monohydric group-containing compound (A-3) having two or more radically polymerizable groups includes 3- (meth) acryloyloxyglycerin mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, and pentaerythritol There are tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, glycidol di (meth) acrylate, dipentaerythritol hepta (meth) acrylate and the like. Furthermore, the equivalent of leaving a hydroxyl group of a trihydroxy compound in a trihydroxy group-containing derivative such as trihydroxyethyl triisocyanurate or trihydroxypropyl isocyanurate in an amount of 0.5 to 1.5 mol, preferably 0.8 to 1.0 mol. In the ratio, a compound obtained by reacting a carboxyl compound derivative having a polymerizable unsaturated group such as acrylic acid, acrylic acid dimer, methyl acrylate or the like by dehydration condensation or transesterification or trihydroxyl group such as trihydroxypropyl isocyanurate The contained derivatives include γ-butyl lactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, D-glucono-1,4-lactone, 1,10-phenanthrene carboractone, 4-pentene-5-olide, 12 Lactones such as dodecanolide or ethylene oxide, B pyrene oxide, cyclic ethers such as tetrahydrofuran, is reacted, the resulting hydroxyl group 3 of the mole,
There is an isocyanuric acid type hydroxyl group-containing compound in which 2 mol of an acid or ester having a radical polymerizable double bond such as (meth) acrylic acid or (meth) acrylate is reacted by dehydration condensation or transesterification. . As a commercially available product, there is Aronix M-215 manufactured by Toagosei Co., Ltd.

Among these, as the monohydric group-containing compound (A-3) having two or more radical polymerizable groups, those having two or three radical polymerizable groups are the tensile elongation at break of the cured coating film. Is very effective. In the case of a monohydroxyl-containing compound having five or more radically polymerizable groups, the cured coating film has low tensile elongation at break. Monohydric group-containing compounds having two or three radically polymerizable groups include 3- (meth)
Acryloyloxyglycerin mono (meth) acrylate, trimethylolpropanedi (meth) acrylate,
Pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, glycidol di (meth) acrylate, and the above-mentioned isocyanuric acid-based hydroxyl group-containing compounds are preferable because of excellent curability and toughness. One or a combination of two or more may be used.

As the monohydric group-containing compound (A-4) having one radical polymerizable group, (meth) having a hydroxyl group
Examples include acryloyl compounds, allyl compounds having a hydroxyl group, vinyl ether compounds having a hydroxyl group, vinyl compounds having a hydroxyl group, and acrylamide compounds having a hydroxyl group.

As the (meth) acryloyl compound having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxybutyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, 3-chloro-2
-Hydroxypropyl (meth) acrylate, 2-hydroxy-3-alkyloxypropyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, poly (ε-caprolactone) mono {2- (meth) acryloxyethyl} ester, ethylene oxide-modified phthalic acid (meth) acrylate,
4-hydroxycyclohexyl (meth) acrylate and the like. Examples of the allyl compound having a hydroxyl group include 2-propen-1-ol and 4-hydroxybutylallyl ether. Examples of the vinyl ether compound having a hydroxyl group include ethylene glycol monovinyl ether, butanediol monovinyl ether, cyclohexane dimethanol monovinyl ether, diethylene glycol monovinyl ether, and hexanediol monovinyl ether. Examples of the vinyl compound having a hydroxyl group include alcohol-terminated polyisoprene TL-20 (manufactured by Kuraray Co., Ltd.) and alcohol-terminated polybutadiene R-15H.
T, R-45HT (manufactured by Idemitsu Petrochemical Co., Ltd.), linoleic acid, linolenic acid, maleic anhydride, maleic acid,
Both terminal or one terminal alcohol group-containing compounds obtained by an esterification reaction of an unsaturated group-containing polycarboxylic acid such as fumaric acid, itaconic acid, or tetrahydrophthalic anhydride with a polyhydric alcohol such as 1,6-hexanediol are used. Examples include saturated polyester and cinnamyl alcohol. Further, as the (meth) acrylamide compound having a hydroxyl group,
N-methylol (meth) acrylamide and the like.

The monohydric group-containing compound (A-4) having one radical polymerizable group includes a (meth) acryloyl compound having a hydroxyl group attached to a primary carbon atom and a diisocyanate compound (A-2). High reactivity, and
Excellent in curability and preferable. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ε-caprolactone) Mono {2- (meth) acryloxyethyl} ester and 4-hydroxycyclohexyl (meth) acrylate are particularly preferred. One or a combination of two or more may be used.

The asymmetric polymerizable linear polyurethane compound (A) is obtained by the following production method. (1) A diol compound (A-1) and a diisocyanate compound (A-2) are reacted so that an isocyanate remains at the terminal, and a monohydric group-containing compound (A-3) having two or more radically polymerizable groups, and A method in which a monohydroxyl-containing compound (A-4) having one radically polymerizable group is sequentially charged and reacted.

(2) 1 having two or more radically polymerizable groups
Reacting a hydroxyl group-containing compound (A-3) and a 1-hydroxyl group-containing compound (A-4) having one radical polymerizable group with a diisocyanate compound (A-2) such that an isocyanate group remains at a terminal; Then, a method in which the diol compound (A-1) is reacted so that no isocyanate group remains.

(3) 1 having two or more radically polymerizable groups
A hydroxyl group-containing compound (A-3), a monohydroxyl group-containing compound (A-4) having one radical polymerizable group, a diisocyanate compound (A-2), and a diol compound (A-
A method in which 1) is obtained by batchwise charging and reacting.

The number of moles of the monohydric group-containing compound (A-3) having two or more radical polymerizable groups: the number of moles of the monohydric group-containing compound (A-4) having one radical polymerizable group The ratio can be appropriately selected, but if it is larger than 2, the crosslink density of the resin composition increases and the elongation at break decreases (the toughness is poor). If it is smaller than 1/2, the composition is not cross-linked by irradiation with a low active energy ray and practical properties cannot be exhibited (the curing property is insufficient).

In the above reaction, for the purpose of increasing the reaction rate, a urethanization catalyst such as tin octylate, dibutyltin dilaurate, lead naphthenate or triethylamine is usually used in an amount of 0.001 to 100 parts by weight of the total amount of the reactants. ~
Use 0.02 parts by weight. If the amount used is large, heat resistance may decrease and coloring may occur. The reaction temperature is set at an upper limit of 90 ° C. and at a temperature at which a temperature rise due to heat generation can be sufficiently suppressed. Usually, it is carried out at 30 to 80 ° C.

The number average molecular weight of the asymmetric polymerizable linear polyurethane (A) of the present invention is selected according to the target tensile modulus of the cured product of the resin composition. To obtain toughness, 500 to 20,000
Is preferable.

Required for a primary coating layer or a unit,
Tensile modulus of elasticity 0.05-1kg / mm ^Two Obtained a cured product of
If the number average molecular weight is 3,500 to 20,000,
3,500 to 18,000 is preferred.

Tensile modulus of elasticity required for secondary coating layer, colored layer, unit, overcoat, etc.
To obtain a cured product having a number average molecular weight of 500 mm ²
~ 3500 is preferred.

The active energy ray-curable resin composition of the present invention contains, in addition to the asymmetrically polymerizable linear polyurethane compound (A), other radically polymerizable unsaturated compounds (B) and additives (C). Is also good.

The other radically polymerizable unsaturated compounds (B) which can be used in the present invention include a diluent (B-1) and a prepolymer (B-2). Good. Because of high reactivity, (meth) acrylic compounds, (meth) acrylamide compounds, and vinyl ether compounds are preferred.

Examples of the diluent (B-1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, and hexyl (meth) acrylate. , Heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate , Dodecyl (meth) acrylate, isododecyl (meth) acrylate, tridecyl (meth) acrylate, isotridecyl (meth) acrylate, pentadecyl (meth) acrylate, isopentadecyl (meth) acrylate Rate, isomyristyl (meth) acrylate, Isobarumichiru (meth) acrylate, isostearyl (meth) acrylate, Neniru (meth) acrylate, Nerorijiru (meth) acrylate,
Hydrocarbon-based monofunctional (meth) acrylates such as farnesyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, behenyl (meth) acrylate, and trans-2-hexene (meth) acrylate; carbitol (meth) A) alkyl-substituted polyalkylene glycol monofunctional (meth) acrylates such as acrylate and butoxyethyl (meth) acrylate;

Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, bicycloheptyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentanyl di (meth) acrylate, tricyclodecyl (meth) Acrylate, bicyclopentenyl (meth)
Acrylate, norbornenyl (meth) acrylate,
Monofunctional (meth) acrylates having an alicyclic structure such as bicyclooctanyl (meth) acrylate, tricycloheptanyl (meth) acrylate, and cholesterol skeleton-substituted (meth) acrylate; benzyl (meth) acrylate; phenoxyethyl (meth) ) Alkyl-substituted (or unsubstituted) phenoxy polyalkylene glycol (meth) acrylates such as acrylates; acrylic acid benzoate of polyalkylene glycol; allyl (meth) acrylate, methallyl (meth) acrylate; glycidyl (meth) acrylate, tetrahydro Furfuryl (meth) acrylate; containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-chloro-2-hydroxyethyl (meth) acrylate Meth) acrylate, 2-hydroxyethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, amino group-containing (meth) acrylates such as acryloyl morpholine;

(Meth) acrylic acid or other acid group-containing (meth)
Acrylates: ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,
Alkylene glycol di (meth) acrylates such as 2-butylene glycol di (meth) acrylate and poly (1,2-butylene glycol) di (meth) acrylate; 1,3-butylene glycol di (meth) acrylate, 1,4 -Butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
1,10-decanediol di (meth) acrylate hydrocarbon diol di (meth) acrylate; obtained by adding 1 mol or more of ethylene oxide and / or propylene oxide and / or butylene oxide to 1 mol of neopentyl glycol Di (meth) acrylate of diol; pivalate ester neopentyl glyco-
Rudiacrylate, caprolactone-modified hydroxypivalic acid ester neopentylglycol diacrylate
G;

For example, di (meth) acrylate of a modified alkylene oxide of a bisphenol such as bisphenol A, F or S, di (meth) acrylate of a hydrogenated bisphenol such as bisphenol A, F or S, bisphenol A or F (S), di (meth) acrylate of alkylene oxide modified product of hydrogenated bisphenol, di (meth) acrylate of alkylene oxide modified product of trisphenol, di (meth) acrylate of hydrogenated trisphenol, hydrogenated tris Di (meth) acrylate of alkylene oxide modified phenols, p,
a di (meth) acrylate of a modified alkylene oxide of p′-biphenol, a di (meth) acrylate of a hydrogenated p, p′-biphenol, a di (meth) acrylate of a modified alkylene oxide of a hydrogenated biphenol,
Di (meth) acrylate of alkylene oxide-modified p, p'-dihydroxybenzophenones, dicyclopentane-based di (meth) acrylate such as Kayarad R684 (manufactured by Nippon Kayaku), tricyclodecane dimethylol di (meth) Phenylene ring, such as acrylate, bisphenol fluorene hydroxy (meth) acrylate,
Cyclohexane ring, cycloalkylene ring such as cyclodecane ring, dicyclopentane ring, bicycloalkylene ring such as dicyclopentene ring, tricycloalkylene ring such as tricyclodecane ring, furan ring, condensed furan ring, thiophene ring, condensed thiophene ring, Pyrrole ring, fused pyrrole ring,
Pyran ring, pyrone ring, quinoline ring, isoquinoline ring, azole ring, naphthalene ring, fluorene ring, azine ring such as triazine ring, 1,3-dioxolane ring, 1,3-dioxane ring, 1,4-dioxane ring, spirane (Meth) acrylate compounds having a cyclic structure such as a ring and a triazolone ring;

Mono (meth) acrylate or poly (meth) acrylate of trimethylolpropane, mono (meth) acrylate or poly (meth) acrylate of glycerin, mono (meth) acrylate or poly (meth) acrylate of pentaerythritol, ditrimethylol Mono (meth) acrylate of propane mono (meth) acrylate, poly (meth) acrylate of dipentaerythritol or mono (meth) acrylate of polyhydric alcohol such as triol, tetraol, hexaol, etc. Poly (meth) acrylates;

Triol mono- and di-ols obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide and / or propylene oxide and / or butylene oxide or a cyclic lactone compound such as ε-caprolactone to 1 mol of trimethylolpropane Alternatively, tri (meth) acrylate, triol monoester obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide and / or propylene oxide and / or butylene oxide or a cyclic lactone compound such as ε-caprolactone to 1 mol of glycerin. , Di- or tri (meth) acrylate, 1 mol or more per mole of pentaerythritol, 1 mol or more of a cyclic ether compound such as ethylene oxide and / or propylene oxide and / or butylene oxide, or ε-cap Mono triol obtained by adding a cyclic lactone compound of a lactone such as di-, tri- or tetra (meth) acrylate, ditrimethylolpropane 1
Triol mono obtained by adding one or more moles of a cyclic ether compound such as ethylene oxide and / or propylene oxide and / or butylene oxide or a cyclic lactone compound such as ε-caprolactone;
1 mol or more of a cyclic ether compound such as ethylene oxide and / or propylene oxide and / or butylene oxide or a cyclic lactone compound such as ε-caprolactone is added to 1 mol of di, tri or tetra (meth) acrylate or dipentaerythritol. Mono (meth) acrylates or poly (meth) acrylates of the obtained triols, or polyhydric alcohols such as triols, tetraols, and hexaols such as poly (meth) acrylate; 2,3-dibromopropyl (meth) acrylate , Tribromophenyl (meth) acrylate,
(Meth) acrylates having a bromine atom such as ethylene oxide-modified tribromophenyl (meth) acrylate and ethylene oxide-modified tetrabromobisphenol A di (meth) acrylate;

Trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, hexadecafluorononyl (meth) Acrylate, hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (Meth) acrylate, 3- (perfluoro-5-
Methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate,
(Meth) acrylates having a fluorine atom such as 3- (perfluoro-8-methyldecyl) -2-hydroxypropyl (meth) acrylate; (meth) acrylamide;
(Meth) acrylamides such as N-hydroxymethyl (meth) acrylamide and alkyl ether compounds of N-hydroxymethyl (meth) acrylamide; N-methylmaleimide, N-phenylmaleimide, N, N'-m-
Maleimides such as phenylenebismaleimide;

Maleic esters such as dimethylmalate, diethylmalate, diisopropylmalate, dibutylmalate, di (2-ethylhexyl) malate, monomethylmalate, monobutylmalate and mono (2-ethylhexyl) malate; Fumaric esters such as dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, diisobutyl fumarate, disec-butyl fumarate, di (2-ethylhexyl) fumarate; dimethyl itaconate, dibutyl itaconate, di Itaconic esters such as (2-ethylhexyl) itaconate, monomethyl itaconate and monobutyl itaconate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, a Vinyl ether, 2-ethylhexyl vinyl ether, octyl vinyl ether, nonyl vinyl ether, dodecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, butoxyethyl vinyl ether, cetyl vinyl ether,
Monovinyl ethers such as phenoxyethyl vinyl ether, allyl vinyl ether, methallyl vinyl ether, glycidyl vinyl ether, 2-chloroethyl vinyl ether, and cyclohexyl vinyl ether, ethylene glycol monovinyl ether or divinyl ether, and triethylene glycol divinyl ether “Rapicure manufactured by I.S.P. DVE-3 ", polyethylene glycol monovinyl ether or divinyl ether, propylene glycol monovinyl ether or divinyl ether,
Polypropylene glycol monovinyl ether or divinyl ether, 1,3-butylene glycol monovinyl ether or divinyl ether, tetramethylene glycol monovinyl ether or divinyl ether, hexamethylene glycol monovinyl ether or divinyl ether, neopentyl glycol monovinyl ether or divinyl ether, trimethylolpropane Monovinyl ether, divinyl ether or trivinyl ether, glycerin monovinyl ether, divinyl ether or trivinyl ether, pentaerythritol monovinyl ether, divinyl ether or trivinyl ether, 1,4-cyclohexane dimethanol monovinyl ether, 1,4-cyclohexane dimethanol divinyl ether IS. . Companies made of Rapikyua CHV
E ", 1 mole or more of ethylene oxide and / or propylene oxide and / or monovinyl ether or divinyl ether of butylene oxide adduct per mole of neopentyl glycol, and 1 mole or more of ethylene oxide and / or propylene per mole of trimethylpropane Monovinyl ether, divinyl ether or trivinyl ether of an oxide and / or butylene oxide adduct, and at least 1 mol of ethylene oxide and / or propylene oxide per 1 mol of bisphenol A, and vinyl ethers such as monovinyl ether and divinyl ether of a propylene oxide and / or butylene oxide adduct ;

Allyl compounds such as diallyl phthalate and triallyl cyanurate; styrene, chlorostyrene, α
-Methylstyrene, divinylbenzene; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl stearate, vinyl adipate, (meth)
Vinyl carboxylate such as vinyl acrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamate; acrylonitrile; limonene, cyclohexene; 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, N- Vinylpyrrolidone; a reaction product of 1 mol of 2-hydroxyethyl (meth) acrylate and 1 mol of phenyl isocyanate, a reaction product of 1 mol of 2-hydroxyethyl (meth) acrylate and 1 mol of n-butyl isocyanate, and the like.

As the prepolymer (B-2), epoxy (meth) acrylate (for example, bisphenol A)
Epoxied rosin, epoxidized soybean oil, epoxy resin such as phenolic bisphenol F type and phenol novolak type
Epoxy resin such as epoxidized polybutadiene and (meth)
Polyester (meth) acrylate (for example, diol components such as ethylene glycol, propylene glycol, diethylene glycol, 1.5-pentanediol, 1.6-hexanediol, and succinic acid, adipic acid, and phthalic acid) (Meth) acrylates of polyester diols composed of dibasic acids, such as hexahydrophthalic acid and tetrahydrophthalic acid, and (meth) acrylates of lactone-modified polyester diols composed of the diol component and dibasic acids and ε-caprolactone or valerolactone. Polycarbonate (meth) acrylate (for example, (meth) acrylate of polycarbonate diol containing 1.6-hexanediol as diol component); siloxane polymer having (meth) acryloyloxy group; There are asymmetrical polymerizable linear polyurethane compound (A) other than the radical polymerizable polyurethane compound (B-2-1) or the like.

The radical polymerizable polyurethane compound (B-2-1) other than the asymmetric polymerizable linear polyurethane compound (A) of the present invention comprises a polyol compound (B-2-2) and a polyisocyanate compound (B-2-2). 3) and a monohydroxyl-containing compound (B-2-4) having a radically polymerizable group, or a polyisocyanate compound (B-2-3) and a monohydroxyl-containing compound (B-2-4) having a radically polymerizable group ) To obtain.

As the polyol compound (B-2-2), besides the diol compound (A-1), glycerin, trimethylolpropane, a modified alkylene oxide of glycerin, and commercially available ADEKA polyether G-
300, G-400, G-700, G-1500, G-
3000B, G-4000 (manufactured by Asahi Denka Kogyo Co., Ltd.), modified alkylene oxide of trimethylolpropane, and commercially available products include ADEKA polyether T-400 and T-40
00 (manufactured by Asahi Denka Kogyo Co., Ltd.), modified caprolactone of triol, and commercially available Placcel 303, 305, and 3
08, L312AL, L320AL and the like (manufactured by Daicel Chemical Industries, Ltd.), pentaerythritol, dimethylolpropanetetraol, modified alkylene oxide of ethylenediamine, and commercial products include:
Adeka polyether EDP-300, EDP-450,
EDP-1100 (manufactured by Asahi Denka Kogyo Co., Ltd.), an alkylene oxide modified product of methyl glucoside, commercially available products include ADEKA polyether MG-575 (manufactured by Asahi Denka Kogyo Co., Ltd.), an alkylene oxide modified product of pentaerythritol, dimethylolpropane tetra Tetraol compounds such as all alkylene oxide modified products, sorbitol alkylene oxide modified products, commercially available products include ADEKA polyether SP-600 (manufactured by Asahi Denka Kogyo Co., Ltd.), sucrose alkylene oxide modified products, commercially available products include: A compound having five or more hydroxyl groups, such as ADEKA polyether SC-800, 1000 (manufactured by Asahi Denka Kogyo Co., Ltd.), may be used. A part or all of the polyol compound (B-2-2) may be replaced with a hydroxyl group-containing compound (A-2-2) having no radical polymerizable group.

Polyisocyanate compound (B-2-3)
As a diisocyanate compound (A-2) and an isocyanate compound having three or more isocyanate groups (A
2-1). Polyisocyanate compound (B-2
Part or all of -3) may be replaced with a monofunctional isocyanate compound. Examples of the monofunctional isocyanate compound include n-butyl isocyanate, phenyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-isocyanatoethyl (meth) acrylate, and the like. Among them, as the polyisocyanate compound (B-2-3), particularly, 2,4-toluylene diisocyanate, 2,6-tolylene diisocyanate,
Isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and tetramethyl xylene diisocyanate are effective.

The monohydroxyl group-containing compound (B-2-4) having a radically polymerizable group includes a monohydroxyl group-containing compound (A-4) having one radically polymerizable group and two or more radically polymerizable groups. There is a monohydric group-containing compound (A-3) having the following formula: 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are effective.

When the cured product of the resin composition of the present invention has a tensile modulus of 1 to 200 kg / mm ² , other radically polymerizable copolymers used in combination with the asymmetrically polymerizable linear polyurethane compound (A) of the present invention. Among the saturated compounds (B), the diluent (B-
1) includes, among others, isobornyl acrylate, dicyclopentenyloxyalkyl acrylate, dicyclopentenyl acrylate, tricyclodecanyl acrylate, tricyclodecanyloxyethyl acrylate,
Monofunctional radically polymerizable unsaturated compound having a cyclic structure such as isobornyloxyethyl acrylate (B-1-1)
Is preferable because of excellent curability and toughness.

Further, a monofunctional radical polymerizable compound having a nitrogen atom selected from acrylamides such as acryloylmorpholine, and N-vinylamides such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide and N-vinylacetamide. The unsaturated compound (B-1-2) is also preferable because it improves toughness and curability.

Ethylene glycol di (meth) acrylate, triethylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, diacrylate of ethylene oxide adduct of bisphenol A, bisphenol A Diacrylate of propylene oxide adduct, tricyclodecane dimethylol diacrylate, acrylic acid adduct of 2,2-di (glycidyloxyphenyl) propane, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, Triac of dipentaerythritol hexaacrylate, tris (2-hydroxyethyl) isocyanurate Polyfunctional radically polymerizable unsaturated compounds (B-) such as acrylate, diacrylate of tris (2-hydroxyethyl) isocyanurate, triacrylate of tris (hydroxypropyl) isocyanurate, ditrimethylolpropanetetraacrylate and ditrimethylolpropanetriacrylate. 1-3) may be used. Polyfunctional radically polymerizable unsaturated compound (B-1-
3) has a feature of increasing the tensile modulus but decreasing the elongation, and therefore it is appropriate to use it in combination with a monofunctional radically polymerizable unsaturated compound as appropriate. Use of the polyfunctional radically polymerizable unsaturated compound (B-1-3) has an effect of reducing swelling deformation due to water absorption.

For the purpose of lowering the tensile modulus, a monofunctional radically polymerizable unsaturated compound (B-1-4) having a homopolymer having a glass transition temperature of 20 ° C. or less may be used. Further, in the prepolymer (B-2), as a radical polymerizable polyurethane compound (B-2-1) other than the asymmetric polymerizable linear polyurethane compound (A), the number average molecular weight was 3
00 to 1500 is good.

In particular, the polyisocyanate compound (B-2)
-3) having a molecular weight of 140 to 500, preferably 1
A monohydric group-containing compound having a radical polymerizable group (B-
As 2-4), a reaction product (B-3) using a monofunctional hydroxy (meth) acrylate having a molecular weight of 100 to 150 and having a hydroxyalkyl group having 3 or more carbon atoms is preferable.

Further, a polyisocyanate compound (B-2)
-3), a monohydric group-containing compound (B-2-4) having a radical polymerizable group, and a polyol compound (B-2-2) as an alkyl diol or polyether having an average molecular weight of 180 to 450 and having 1 or more carbon atoms. Reaction products (B-4) using diols and polyalkyl polyether diols are preferred. (B-3) and (B-4) may be used alone or in combination with (A).

In (B-3), when the polyisocyanate compound (B-2-3) has three or more functional groups or has a molecular weight of more than 500, the viscosity of the composition increases, and high-speed processability and curability deteriorate. . In the monofunctional hydroxy (meth) acrylate in which the monohydroxyl group-containing compound (B-2-4) having a radical polymerizable group is a hydroxyalkyl group having 2 or less carbon atoms, the viscosity of the composition increases, and the high-speed processability increases. become worse.

In (B-4), if the average molecular weight of the polyol compound (B-2-2) exceeds 500, the toughness is poor. The use of alkyl diols, polyether diols, and polyalkyl polyether diols having an average molecular weight of 180 to 500 and having 1 or more carbon atoms is particularly preferable because of excellent curability and high-speed processing characteristics. Average molecular weight 180-500
As an alkyl diol having 1 or more carbon atoms, polyether diol, and polyalkyl polyether diol,
1,4-butanediol, neopentyl alcohol,
1,6-hexanediol, 3-methylpentanediol, nonanediol, propylene oxide or 1,2
-Polyol which is a polymer of butylene oxide, propylene oxide, diol which is a copolymer of 1,2-butylene oxide and tetrahydrofuran, 12-hydroxystearyl alcohol, alkylene oxide of bisphenol A, alkylene oxide of hydrogenated bisphenol A, bisphenol A epoxy acrylate and the like.

As the monohydric group-containing compound (B-2-4) having a radical polymerizable group, monofunctional hydroxy (meth) acrylate, which is a hydroxyalkyl group having 3 or more carbon atoms, has a reduced viscosity of the composition. It is preferable because of its good high-speed workability. If the polyisocyanate compound (B-2-3) and the polyol compound (B-2-2) have low viscosities, a monofunctional hydroxy (meth) acrylate which is a hydroxyalkyl group having 2 carbon atoms may be used. Absent.

When the tensile modulus is 1 to 200 kg / mm ² , the asymmetric polymerizable linear polyurethane compound (A) and the diluent (B-1) are used in a total of 100% by weight. (A) is 20 to 80% by weight
Is preferred. If the amount is less than 20% by weight, sufficient elasticity, toughness, and curability cannot be obtained. 30-70% by weight
It is excellent in elastic modulus, toughness, curability and high-speed processability, and is particularly preferable. As long as the prepolymer (B-2) does not deviate from the effective range of the asymmetric polymerizable linear polyurethane compound (A), the asymmetric polymerizable linear polyurethane compound (A) is replaced with the prepolymer (B-2). And may be used. If the prepolymer (B-2) is less than 10% by weight, the elastic modulus is low, and if it exceeds 45% by weight, the toughness is reduced. It is particularly preferable to add in the range of 15 to 30% by weight because it has excellent toughness, curability and high-speed processability.

The diluent (B-1) is preferably from 20 to 80% by weight. If the diluent is less than 20% by weight, the viscosity increases and the high-speed processability deteriorates. If it exceeds 80% by weight, sufficient elasticity, toughness and curability cannot be obtained, and 30 to 70% by weight.
Has excellent elasticity, curability, toughness, and high-speed workability.
Particularly preferred. In the diluent (B-1), a monofunctional radically polymerizable unsaturated compound having a cyclic structure (B-1-
1) is preferably 0 to 30% by weight, and at 30% by weight or more,
Poor toughness and poor high-speed workability. Monofunctional radically polymerizable unsaturated compound having a nitrogen atom (B-1-2) 0
If it is 30% by weight or more, the toughness is inferior and the high-speed workability is poor. The polyfunctional radically polymerizable unsaturated compound (B-1-3) is preferably 0 to 40% by weight, and if it is 40% by weight or more, the elongation is reduced. Within the range of 20 to 80% by weight, (B-1-1), (B-1-2), (B-
A diluent (B-1) other than 1-3) may be used.

When the cured product of the resin composition of the present invention has a tensile modulus of 0.05 to 1 kg / mm ² , other radical polymerization used in combination with the asymmetric polymerizable linear polyurethane compound (A) of the present invention. As the diluent (B-1) in the unsaturated unsaturated compound (B), a monofunctional radically polymerizable unsaturated compound (B-1-4) having a glass transition temperature of a homopolymer of 20 ° C. or less is a tensile elasticity. The rate is low and effective.
The glass transition temperature is described in Polymer Handbook and other documents, and in catalogs of reactive diluents.
Specifically, lauryl acrylate, isodecyl acrylate, isostearyl acrylate, lauryl alcohol ethoxy acrylate, epoxy stearyl acrylate, 2- (1-methyl-4-dimethyl) butyl-5-methyl-7-
Dimethyl octyl acrylate, phenoxy ethyl acrylate, phenoxy ethoxy ethyl acrylate, phenol polyalkoxy acrylate, nonyl phenoxy ethyl acrylate, nonyl phenol polyethylene oxide modified acrylate, nonyl phenol polypropylene oxide modified acrylate, butoxy polypropylene glycol acrylate, tetrahydrofurfuryl alcohol lactone modified acrylate, lactone modified Examples include 2-hydroxyethyl acrylate and 2-ethylhexyl carbitol acrylate. In particular, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, phenol polyalkoxy acrylate, nonylphenoxyethyl acrylate, nonylphenol ethylene oxide-modified acrylate, and nonylphenol polypropylene oxide-modified acrylate are effective.

Further, a monofunctional radically polymerizable unsaturated compound having a hydroxyl group, a carboxylic acid group, or a cyclic ether group (B
The monofunctional radically polymerizable unsaturated compound (B-1-2) having -1-5) and a nitrogen atom is effective in improving the adhesion to glass and the curability. Examples of the radical polymerizable unsaturated compound having a hydroxyl group include 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and hydroxybutyl vinyl ether. Radical polymerizable unsaturated compounds having an acid group include acrylic acid dimer, ω-carboxy-polycaprolactone monoacrylate, and monofunctional radical polymerizable unsaturated compounds having a cyclic ether group include tetrahydrofurfuryl acrylate. .

For the purpose of adjusting the tensile modulus, a polyfunctional radically polymerizable unsaturated compound (B-1-3) may be used. When the tensile modulus is 0.05 to 1 kg / mm ² , the asymmetrically polymerizable linear polyurethane compound (A) and the diluent (B-1) are used in a total of 100% by weight. A) is 35 to 95% by weight
Is preferred. If it is less than 35% by weight, sufficient curability cannot be obtained, and if it exceeds 95% by weight, the viscosity increases and the high-speed processability deteriorates. The range of 40 to 85% by weight is excellent in curability and high-speed processability, and is particularly preferable. Prepolymer (B-2)
May be used as long as the effective range of the asymmetric polymerizable linear polyurethane compound (A) is not deviated from the effective range of the asymmetric polymerizable linear polyurethane compound (A).

The diluent (B-1) is preferably from 5 to 65% by weight. If the diluent is less than 5% by weight, the viscosity increases and the high-speed processability deteriorates. If it exceeds 65% by weight, curability cannot be obtained, and 15 to 60% by weight of the rubber composition has elasticity, curability, toughness,
It is particularly preferable because it has excellent high-speed workability. Diluent (B-
In 1), a monofunctional radically polymerizable unsaturated compound having a homopolymer having a glass transition temperature of 20 ° C. or lower (B-1-4)
Is preferably 0 to 60% by weight, and if it is 60% by weight or more, the curability is inferior and the high-speed processability is poor. Monofunctional radically polymerizable unsaturated compound having a nitrogen atom (B-1-2) 0 to 20
When the content is 20% by weight or more, the water resistance is poor. Polyfunctional radically polymerizable unsaturated compound (B-1-3) 0-2
0% by weight is good, and if it is 20% by weight or more, elongation decreases.
If it is within the range of 15 to 65% by weight, (B-1-4)
Diluents other than (B-1-2) and (B-1-3) (B-
1) may be used.

The active energy rays used herein include ultraviolet rays, electron beams, ionizing radiation such as α-rays, β-rays, and γ-rays, microwaves, high-frequency waves, and the like. , Any kind of energy is acceptable. Visible light, infrared light, or laser light may be used. Examples of a device that generates ultraviolet light include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, a short arc lamp, a helium / cadmium laser, an argon laser, and an excimer UV lamp. (172 nm, 185 nm, 222 nm, 254 n
m, 308 nm, etc.), and may be selected in consideration of the absorption wavelength of a compound that generates a radically active species.

In the case where two layers are continuously cured, it is effective to change the irradiation wavelengths of the first layer and the second layer to completely cure the layers. When irradiating the second layer, in order for light to reach the first layer, a lamp having a longer wavelength may be used for the second layer. For example, the first layer is irradiated with a 254 nm main wavelength lamp (for example, a high pressure mercury lamp), and the second layer is irradiated with a 365 main wavelength lamp (for example, a metal halide lamp).

Electron beams are generated by Iwasaki Electric Co., Ltd. Electro-Curtain, Sumitomo Heavy Industries, Ltd. Broad Beam,
There are Curetron manufactured by Nissin High Voltage, Lyocure manufactured by Toyo Ink, Mini-EB manufactured by American International Technology, Electron Cure manufactured by Allied Signal Inc., and the like. When an electron beam hits the glass, lattice defects are generated, which is not preferable.
It is effective when used for curing a layer above the next coating layer. The acceleration voltage may be calculated in consideration of the specific gravity and the thickness of the coating layer. When used when solidifying the UV ink layer, a UV ink coating layer having good adhesion to the underlayer can be provided.

As another additive (C), there is a photopolymerization initiator (C-1). As a photopolymerization initiator (C-1), an intramolecular bond-cleaving initiator in which a bond is cleaved in a molecule by light to generate a polymerization-initiating active species (radical active species);
There is an intermolecular hydrogen abstraction initiator that causes a reaction or the like between molecules to generate an active species for polymerization initiation (radical active species).

Examples of the intramolecular bond-cleaving initiator include, for example, diethoxyacetophenone (FIRSTCURE DEAP manufactured by First Chemical Company, USA), 1- {4- (2
-Hydroxyethoxy) phenyl {-2-hydroxydi-2-methyl-1-propan-1-one} Circa Specialty Chemical (hereinafter abbreviated as CSC) Irgacure 2959), 2-methyl-2-morpholino (4 −
Methylthiophenyl) propan-1-one (Irgacure 907 manufactured by CSC), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369 manufactured by CSC), 2-hydroxy- 2-methyl-1-phenylpropan-1-one (C
SC Darocur 1173), 1-hydroxycyclohexyl phenyl ketone (CSC SC Irgacure 18)
4), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Darocur 1116 manufactured by CSC), benzyldimethyl ketal (CSC
Irgacure 651), a mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone (CS
C, Irgacure 500), 4- (2-acryloyl-oxyethoxy) phenyl-2-hydroxy-2-propyl ketone (ZLI3331 from CSC), oligo {2-hydroxy-2-methyl-1- "4- ( 1-methylvinyl) phenyl ”propanone, molecular weight of 2000 or less (Esacure KIP100 manufactured by Lamberti),
Acetophenones such as

Benzoin, 3,6-bis (2-methyl-
Benzoin compounds such as 2-morpholinopropionyl) -9-n-octylcarbazole, benzoin isopropyl ether and benzoin isobutyl ether;
Trimethylbenzoyldiphenylphosphine oxide (Lucillin TPO, LR8953 manufactured by BASF), 2,
4,6-trimethylbenzoylethoxyphenylphosphine oxide (Lucillin TPO-L manufactured by BASF),
Bisacylphosphine oxide and 2-hydroxy-2
A mixture with -methyl-1-phenylpropan-1-one (CGI 1700 manufactured by CSC), acylphosphine oxides such as Irgacure 819 manufactured by CSC, CGI403 manufactured by CSC, benzyl, methylphenylglyoxyester, 3,3 ', 4,4',-tetra (t-butylperoxycarbonyl) benzophenone (BTTB manufactured by NOF Corporation) and the like.

Examples of the intermolecular hydrogen abstraction initiator include benzophenone (Kayacure BP- manufactured by Nippon Kayaku Co., Ltd.).
100), methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide (Kayacure BMS manufactured by Nippon Kayaku Co., Ltd.), acrylated benzophenone (UCB) Ubecryl P36), 2,
A mixture of 4,6-trimethylbenzophenone and 4-methylnzophenone (Esacure TZ manufactured by Lamberti)
T) 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-
Benzophenones such as 4-methoxybenzophenone, 2
-Isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4
Thioxanthones such as dichlorothioxanthone, Michler's ketone, aminobenzophenones such as 4,4'-diethylaminobenzophenone, 10-butyl-2-chloroacridone, 2-ethylanthraquinone (Kayacure 2-EAQ manufactured by Nippon Kayaku Co., Ltd.), 9,10-phenanthrenequinone, camphorquinone and the like.

Among them, 1-hydroxycyclohexyl phenyl ketone, thioxanthone and thioxanthone derivatives, 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl]
-2-morpholinopropane-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl)-
2,4,4-trimethylpentylphosphine oxide,
One or a mixture of two or more selected from 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole and 2,2-dimethoxy-2-phenylacetophenone is preferred. In particular, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2-benzyl- having a morpholino group
2-dimethylamino-1- (4-morpholinophenyl)
A photoinitiator (C-1) for curing butanone-1,3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole with a resin composition having a thickness of 50 μm or more; Inside, 30 parts by weight or less, 5
When the thickness of less than 0 μm is cured, adding 80 parts by weight or less to the photopolymerization initiator (C-1) is effective because the curing rate is increased even in an atmosphere having an oxygen concentration of 1000 ppm or more.

The solid-state photoinitiator was previously prepared as 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- "4-
(1-methylvinyl) phenyl ”propanone, molecular weight 2
2,000 or less {, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, a liquid photoinitiator such as benzophenone and the like, when used in a liquid state, the workability is improved and it is effective.

When the resin composition of the present invention is irradiated with ultraviolet rays, the resin composition is cured only by adding the above-mentioned photopolymerization initiator (C-1). However, in order to further improve the curability, a photosensitizer is used in combination. Is preferred. Such photosensitizers include, for example, triethanolamine, methyldiethanolamine,
Triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), isoamyl 4-dimethylaminobenzoate (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.),
There are amines such as (2-dimethylamino) ethyl benzoate, (n-butoxy) ethyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate.

The proportion of the photopolymerization initiator (C-1) used is 0.0% in the active energy ray-curable resin composition of the present invention.
The content is preferably in the range of 5 to 10.0% by weight.
If the content is more than 10% by weight, the ultraviolet rays are prevented from penetrating into the inside of the coating film, and the curing becomes insufficient. Similarly, the amount of the photosensitizer is preferably in the range of 0.05 to 10% by weight based on the active energy ray-curable resin composition of the present invention.

In addition, as an additive (C), unsaturated 2
Saturated compound having no heavy bond (C-2), pigment / dye (C-3), antioxidant (C-4), ultraviolet absorber (C
-5), a light stabilizer (C-6), a plasticizer (C-7), a non-reactive compound (C-8), a chain transfer agent (C-9), a thermal polymerization initiator (C-10), Anaerobic polymerization initiator (C-11), polymerization inhibitor (C-12), inorganic filler / organic filler (C-
13) an adhesion improver such as a coupling agent (C-14);
Heat stabilizer, antibacterial / antifungal agent, flame retardant (C-15), matting agent, antifoaming agent, leveling agent, wetting / dispersing agent, anti-settling agent, thickener / anti-sagging agent, color separation prevention An agent, an emulsifier, an anti-slip / scratch agent, an anti-skinning agent, a desiccant, an antifouling agent, an antistatic agent, and a conductive agent (electrostatic aid) may be added. An organic solvent (C-16) may be added as necessary, but in this case, it is preferable to remove the organic solvent before curing with active energy rays. A silicone compound (C-17) may be added to improve the slipperiness of the cured coating film.

A saturated compound having no unsaturated double bond (C
-2) indicates a liquid or solid oligomer or resin having low or no radical reactivity, for example,
Liquid polybutadiene, liquid polybutadiene derivative, liquid chloroprene, liquid polypentadiene, dicyclopentadiene derivative, saturated polyester oligomer, polyether oligomer, liquid polyamide, polyisocyanate oligomer, xylene resin, ketone resin, petroleum resin, fluorine-based oligomer / resin, silicon Oligomers / resins, polysulfide oligomers / resins, cellulose derivatives such as nitrocellulose, benzylcellulose, acetylcellulose, acetylbutylcellulose, vinyl chloride / vinyl acetate copolymer resins, other vinyl chloride copolymer resins, vinylidene chloride or copolymers thereof Polymerized resin, rack or copearl resin, fatty acid modified urethane resin,
Lacquer, oxidized polymer resin such as oil-modified phenolic resin, alkyd resin, amino alkyd resin, epoxy resin / fatty acid ester, epoxy resin, polyurethane resin,
There are acrylic resin, acrylic resin / polyurethane, vinyl resin and the like. These non-reactive oligomers and resins are
It may have a functional group such as a halogen, an epoxy group, an amino group, a hydroxyl group, a thiol group, an amide group, a carboxyl group, a phosphoric acid group and a sulfonic acid group.

As pigments and dyes (C-3), oil-disintegrating dyes are suitable because of their excellent solubility, but any pigments and dyes may be used. After the pigment is dispersed in the resin component,
It is good to remove a large particle size by a filter. For the secondary coating layer, for the UV ink or for the material for coating the outer layer, a resin composition containing no pigment having a particle size of 5 μm or more does not affect the transmission loss of the coated optical fiber,
It is valid.

As the antioxidant (C-4), 2,6-
Di-t-butyl-p-cresol, butylated hydroxyanisole, stearyl-propionate-β- (3,5-
Di-t-butyl-4-hydroxyphenyl), n-octadecyl-3- (4-hydroxy-3 ′, 5′-di-
(t-butylphenyl) pyropionate, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzylmalonate, 2,4,6-tri-t-butylphenol, 2,2′-methylene-bis (4 -Methyl-6-
t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), NN-bis-3- (3 ′, 5 ′)-di-t-
Butyl-4-hydroxyphenyl) propionylhexamethylenediamine, 1,6 hexanediol bis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2, 2-thio-diethylene-bis- [3- (3,5-di-t-butyl-4-
(Hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-
4-hydroxy-5-methylphenyl) propionyloxyethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2′-ethylidene-bis- (2,4-di-t- Butylphenol),

1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl) propionate] methane,
1,1,3-tris- (2-methyl-4-hydroxy-
5-t-butylphenylbutane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-di-t-butyl-4-hydroxybenzyl) benzene, tris (3
5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ', 5'-di-t-butyl-4'-hydroxyhydro-cinnamyloxyl) ethyl] isocyanurate, tris -(4-t-butyl-2,6-di-methyl-3-hydroxybenzyl) isocyanurate, tetrakis- [methylene-3-
(3 ′, 5′-Di-t-butyl-4′-hydroxy-
[Phenyl] propionate] -methane and other phenolic antioxidants; dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate and other sulfur-based antioxidants; triphenyl phosphite, phosphorus phosphite Diphenylisdecyl acid, tris (nonylphenyl) phosphite, 4,4'-butylidene phosphite
There are phosphorus antioxidants such as bis (3-methyl-6-t-butylphenyl-ditridecyl) and phosphite cyclic neopentanetetraylbis (octadecyl). Among them, phenolic antioxidants are particularly effective because they have a strong effect of preventing decomposition at high temperatures.

ADK STAB AO-50, AO manufactured by Asahi Denka Co., Ltd.
-60, AO-75, AO-80 and Irganox 1222 manufactured by Ciba Specialty Chemicals are effective. The compounding amount of the antioxidant (C-4) is preferably 0.1 to 10% by weight in the resin composition of the present invention. When the content is 0.1% by weight or less, the antioxidant function is weak, and when the content is 10% by weight or more, the curability is significantly reduced.

As the ultraviolet absorbent (C-5), 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ′ −
Dihydroxy-4-methoxybenzophenone, 2,4-
Dihydroxybenzophenone, 2-hydroxy-4-methoxy-4′-chlorobenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,
2 ', 4,4'-tetradihydroxybenzophenone,
Benzophenone ultraviolet absorbers such as 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone,
(2′-hydroxy-5-methylphenyl) benzotriazole, 2 (2′-hydroxy-3 ′, 5′-di-t
-Butylphenyl) benzotriazole, 2 (2'-hydroxy-3'-t-butyl-5'-methylphenyl)
Benzotriazole, 2 (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2 (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5
-Chlorobenzotriazole, 2 (2'-hydroxy-
Benzotriazole-based ultraviolet absorbers such as 3 ′, 5′-dibutylphenyl) -6-chlorobenzotriazole;

Phenylsalicylate, para-t-
Phenylsalicylic ester UV absorbers such as butylphenylsalicylate and para-octylphenylsalicylate, ethyl-2-cyano-3,3-diphenylacrylate, methyl-2-carbomethoxy-
Cyanoacrylate-based ultraviolet absorbers such as 3- (paramethoxy) -acrylate, nickel- [2,2′-thiobis- (4-t-octyl) -phenolate] -n-butylamine, nickel dibutyldithiocarbamate, cobalt dicyclohexyldithio Metal complex salt ultraviolet absorbers such as phosphate, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl)-
Triazine-based ultraviolet absorbers such as 5-octyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2
Ogizanilide-based UV absorbers such as ethoxy-2'-ethylogizanic acid bisanilide; inorganic UV absorbers such as cerium oxide; resorcinol-monobenzoate; 2'-ethyl-hexyl-2-cyan;
There are other ultraviolet absorbers such as phenylcinnamate.

In particular, benzotriazoles are preferred.
Tinuvin P, 2 manufactured by Ciba Specialty Chemicals
34, 320, 326, 327, 328, 329, 21
3 is effective. The added amount of the ultraviolet absorber (C-5)
In the resin composition of the present invention, the range of 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight is preferable because the curability is not reduced and an ultraviolet absorbing effect can be obtained.

As the light stabilizer (C-6), bis (1,2,2,6,6-pentamethyl-4-piperidyl) separate, bis (2,2,6,6-tetramethyl-4-) Piperidyl) separate, 2- (3,5-di-t)
Bis (1,2,2,6,6-pentamethyl-4) -butyl-4-hydroxybenzel) -2-n-butylmalonate
-Piperidyl), dimethyl-1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine hybrid, poly [16- (1,
(1,3,3-tetramethylbutyl) imino-1.3.5
-Triazine-2,4-diyl], [(2,2,6,6
-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], 1- [2- [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyloxy) ethyl] -4- [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionyloxy] -2,
2,6,6-tetramethylpiperidine, (mixed 1,2,2,6,6-pentamethyl-4-piperidyl /
Tridecyl) -1,2,3,4-butane tetracarboxylate, mixed [1,2,2,6,6-pentamethyl-4-piperidyl / beta, beta, beta ^'- tetramethyl -
3,9- [2,4,8,10-tetraoxaspiro (5,5) undecashi] diethyl] diethyl 1-1,
2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)
There are hindered amine light stabilizers such as -1,2,3,4-butanetetracarboxylate.

Cinna Specialty Chemicals Co., Ltd. Tinuvin 144, 292, 622LD, LS770, Asahi Denka ADK STAB LA-52, LA-57, LA-6
2, LA-67, LA-63, LA-68, LA-77
Is good. The hindered amine light stabilizers may be used alone or in combination of two or more. The amount of the light stabilizer (C-6) in the resin composition of the present invention is:
The range of 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight is preferable because the curability is not reduced and a light stabilizing effect can be obtained.

Examples of the plasticizer (C-7) include adipic acid compounds such as di- (2-ethylhexyl) adipate and diisodecyl adipate; azelaic acid compounds such as di (2-ethylhexyl) azelate; Phthalates such as diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, di-n-heptyl phthalate, diisodecyl phthalate, butylphthalylbutyl glycolate Acid compounds, sebacic acid compounds such as dioctyl sebacate, trimellitic acid compounds such as tris- (2-ethylhexyl) trimellitate, phosphoric acid compounds such as triphenyl phosphate and tricresyl phosphate, and epoxidation Examples include soybean oil, medium molecular weight polyester, and chlorinated paraffin.

The non-reactive compound (C-8) includes n-
Docosan, 2,6,10,14-tetramethylpentadecane, eicosan, α-farnesene, squalane, squalene, n-dodecylcyclohexane, stearylcyclohexane, n-dodecylbenzene, o-terphenyl and m-terphenyl.

Examples of the chain transfer agent (C-9) include dodecyl mercaptan, ethyl mercapto acetate, butanediol dithiopropionate, pentaerythritol tetrakis (β-thiopropionate), triethylene glycol dimercaptan and the like. Chain transfer agent (C-
The compounding amount of 9) is 0.05 to 1 in the resin composition of the present invention.
0 parts by weight, preferably in the range of 0.1 to 5 parts by weight, can lower the tensile modulus without lowering the curability. Among the chain transfer agents (C-9), mercapto silane coupling agents increase the adhesive strength with glass and have a function of chain transfer, so that the tensile modulus is low and the adhesiveness with glass is strong. It is effective to add it to the resin composition for the primary coating material, which is required to have this. Examples of mercapto silane coupling agents include A-189 and AZ-612 manufactured by Nippon Unicar Co., Ltd.
9 is good.

As the thermal polymerization initiator (C-10),
4-dichlorobenzoyl peroxide, benzoyl peroxide, 1,1-di (t-butylperoxy)-
3,3,5-trimethylcyclohexane, n-butyl-
There are peroxides such as 4,4'-di (t-butylperoxy) valerate and dicumyl peroxide, azo compounds such as 7-azobisisobutylnitrile, tetramethylthiuram disulfide and the like. Thermal polymerization initiator (C-10)
Is 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight in the resin composition of the present invention. Addition within this range is effective without causing a decrease in coating film strength in an environmental test. When the amount is less than 0.1 part by weight, there is no effect, and when it exceeds 2 parts by weight, it remains in the coating film and the environmental resistance is reduced. As the thermal polymerization initiator (C-10), the half-life is 70 ° C.
It is better to choose one at 100 ° C. If it is lower than 70 ° C., the storage stability is poor, and if it is 100 ° C., the curability is inferior. The thermal polymerization initiator (C-10) is decomposed by infrared light simultaneously irradiated from a lamp when irradiating ultraviolet rays, and generates a polymerization initiation radical. Alternatively, a step of heating the coating film (for example, a step of irradiating infrared light) before or after irradiation with ultraviolet light is preferably performed to decompose and generate polymerization initiation radicals.

Examples of the anaerobic polymerization initiator (C-11) include cumene hydroperoxide and t-butyl hydroperoxide. As a polymerization accelerator for anaerobic polymerization, dibenzenesulfonamide, tertiary amine, 1,2,3,4
-Tetrahydroquinoline and the like. Anaerobic polymerization initiator (C
The amount of -11) used is 0.05 to 5% by weight in the resin composition. Particularly preferably, 0.1 to 3% by weight. The amount of the polymerization accelerator used in anaerobic polymerization is 0.1 to 10% by weight in the resin composition. Particularly preferably, it is 0.5 to 5% by weight.

Examples of the polymerization inhibitor (C-12) include quinones, nitrosos, and sulfur compounds. For example, hydroquinone, hydroquinone monomethyl ether, p-
Benzoquinone, 2,5-di-tert-butyl-p-benzoquinone, nitrosobenzene, tert-butylhydroquinone, pyrogallol, phenothiazine, N, N-
Di-sec-butyl-p-phenylenediamine, N-nitrosophenylhydroxyamine ammonium salt, tris (N-nitroso-N-phenylhydroxyamine),
Aluminum salts and the like. The compounding amount of the polymerization inhibitor (C-12) is 0.001 to 0.2 part by weight, preferably 0.001 to 0.1 part by weight in the resin composition of the present invention. If the amount is small, there is no effect, and the storage stability decreases. If the amount is large, the curability decreases.

The inorganic filler and the organic filler (C-13)
Generally used to improve mechanical properties such as strength, cushioning, and slipperiness.

Examples of the inorganic filler include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, glass, Mica, barium sulfate, alumina white, zeolite, silica balloon, glass balloon and the like. By adding and reacting a silane coupling agent, a titanate coupling agent, an aluminum coupling agent and a zirconate coupling agent to the inorganic filler, a halogen group, an epoxy group, an amino group, a hydroxyl group, a thiol It may have a functional group such as a group, an amide group, a carboxyl group, a phosphoric acid group and a sulfonic acid group.

As the organic filler, benzoguanamine resin, melamine resin, benzoguanamine / melamine resin,
Urea resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, crosslinked polystyrene, polydivinylbenzene, styrene / divinylbenzene copolymer, acrylic copolymer, crosslinked acrylic resin , Polymethyl methacrylate resin, vinylidene chloride resin, fluororesin, nylon 12, nylon 11, nylon 6/66,
There are phenol resin, epoxy resin, urethane resin, polyimide resin and the like. The organic filler may have a functional group such as a halogen group, an epoxy group, an amino group, a hydroxyl group, a thiol group, an amide group, a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

The inorganic filler / organic filler (C-13)
When added to the resin composition for the outermost layer, workability such as slipperiness is improved and is effective. Inorganic filler, organic filler (C-1
When the optical fiber is connected in a state where the resin composition coating layer containing 3) is coated, the particle diameter of the inorganic filler and the organic filler (C-13) contained is 10 μm or less, preferably 5 μm or less.
It is important that the connection can be controlled stably to μm or less and can be connected stably. When an optical fiber is connected in a state where the resin composition coating layer containing an inorganic filler and an organic filler (C-13) is peeled off, if the particle size is smaller than the coating thickness with respect to the particle size, an almost smooth coating surface is obtained. can get. When it is desired to make the coated surface uneven, an inorganic filler or an organic filler (C-13) having a particle size larger than the coating thickness may be used.

As the coupling agent (C-14), γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, hexamethyl Silane coupling agent having an amino group such as silazane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxy A silane coupling agent having an epoxy group such as silane,

A silane coupling agent having a mercapto group such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane;
Silane coupling agents having a halogen group such as -chloropropyltrimethoxysilane, silane coupling agents having a methacryloxy group such as γ-methacryloxypropyltrimethoxysilane γ-methacryloxypropylmethyldimethoxysilane, γ-isocyanatopropyltri A silane coupling agent such as a silane coupling agent having an isocyanate group such as methoxysilane and γ-isocyanatopropyltriethoxysilane;
Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyldimethacrylisostearoyl titanate, isopropyldiacrylisostearoyl titanate, isopropyltriisostearoyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrolate) (Phosphate) titanate-based coupling agents such as ethylene titanate, isopropyl tridodecylbenzenesulfonyl titanate, and isopropyl tricumylphenyl titanate; aluminum-based coupling agents such as acetoalkoxy aluminum diisopropylate;
Zirconium-based coupling agents such as acetylacetone-zirconium complex and the like can be mentioned. In particular, a silane coupling agent is effective.

The amount of the coupling agent (C-14)
In the resin composition of the present invention, the range of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight has the effect of increasing the adhesion to the base. Conversely, if the amount is too large, the adhesion decreases. The addition of the coupling agent (C-14) has an effect of increasing the adhesion to the UV cured resin cured layer in addition to the effect of increasing the adhesion to glass. A resin containing a silane coupling agent having an amino group, a silane coupling agent having an epoxy group, and a silane coupling agent having a mercapto group on a cured coating film irradiated with ultraviolet rays in an atmosphere having an oxygen concentration of 1000 ppm or more. When a coating film of the composition is formed, the adhesion is high. When a silane coupling agent having an isocyanate group is added, the adhesion is high even with a coating film cured in an atmosphere having an oxygen concentration of 1000 ppm or less.

Examples of the flame retardant (C-15) include phosphoric esters such as tricresyl phosphate, cresylphenyl phosphate, octyldiphenyl phosphate, tris (chloroethyl) phosphate, and tris (2,3-dichlorophosphate). Propyl), tris (2,3-dibromopropyl) phosphate, halogenated phosphates such as 2,3-dibromopropyl-2,3-chloropropyl phosphate, chlorinated paraffin, perchloropentacyclodecane, hexa Bromocyclododecane, hexabromobenzene, tetrabromobisphenol A derivatives, low molecular weight halides such as decabromobisphenyl ether, chlorinated polyethylene, brominated polycarbonate, brominated epoxy, brominated polystyrene, brominated polybenzyl acrylate, bromine Polyphenylene oxide, etc. Reactive halides such as high molecular weight halides, brominated epoxies, brominated phenols, brominated phenyl (meth) acrylates, brominated styrenes, tetrabromophthalic anhydride, diallyl brominated phthalates, chloroendoic acids, and phosphorus-containing Polyols, polyurethanes of phosphorus-containing polyols, inorganic substances such as antimony trioxide, sodium antimonate, tin oxide, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, zinc borate, molybdenum, zinc stannate, Examples include nitrogen compounds such as melamine, urea, brominated guanamine, and phosphazene compounds, silicone powder, and expandable graphite. Although it may be used alone, the effect is enhanced when used in combination. Halogen and antimony, halogen and phosphorus,
A combination of phosphorus and nitrogen is effective.

If the additive (C) is difficult to mix with the resin composition of the present invention, the solvent (C) may be added if necessary.
-16) is used. As the solvent (C-16) to be used,
Aromatic hydrocarbons such as toluene and xylene, methanol,
Examples include alcohols such as ethanol and isopropyl alcohol, esters such as ethyl acetate, ethicello, methicello, and cellosolve acetate, and ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. One of these solvents may be used alone.
You may mix and use more than seeds.

As the silicone compound (C-17),
Dimethyl polysiloxane (silicone) and modified silicone are effective. As dimethylpolysiloxane, KF96 manufactured by Shin-Etsu Chemical Co., Ltd. has a viscosity of 10 cSt to 1,000,000 cS.
t is valid. As the modified silicone, those obtained by introducing an organic group other than a methyl group into the terminal and / or the side chain of dimethylpolysiloxane (silicone) are preferable. Examples of the organic group to be introduced include an amino group, a hydroxyl group, a carboxyl group,
(Meth) acrylic group, alkoxy (meth) acrylic group, glycidyl group, mercapto group, polyether group, phenyl group, alkyl group, higher fatty acid ester group, alkoxy group, fluorine-substituted alkyl group, fluorine-substituted alkoxy group and amino group, Hydroxyl groups are good. In particular, a modified silicone having a long-chain polyether group, an alkyl group, a higher fatty acid ester group, an alkoxy group, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxy group introduced therein has good compatibility with the resin composition of the present invention and is excellent. Surface properties are obtained. In particular, glycidyl group, (meth) acrylic group, higher fatty acid ester group,
The alkylene oxide group (particularly, a copolymer group of ethylene oxide and propylene oxide) is preferable because it has good compatibility with the resin composition of the present invention and excellent surface properties can be obtained. The organic groups to be introduced may be used alone or in combination.

The compounding amount of the silicone compound (C-17) is in the range of 0.05 to 40 parts by weight, preferably 0.1 to 30 parts by weight in the resin composition of the present invention. In small quantities,
There is no effect of improving the slipperiness, and if it is more than 40 parts by weight, the mechanical properties of the coating film deteriorate. Silicone compound (C-17)
May be used alone, but a combination of two or more is effective.

In the resin composition of the present invention, the asymmetrically polymerizable linear polyurethane compound (A), the other radically polymerizable unsaturated compound (B) and the additive (C) may be added in any order. Generally, (B) and then (C) are added to (A) while heating and stirring. It is effective to add (B) or (C) in a solid or powder form after dissolving or uniformly dispersing it in a part of (A), (B) or (C) in advance. (B) or (C) which does not affect the production reaction of (A)
It may be added before or during the production of (A).

The resin composition of the present invention adjusted as described above has a viscosity at the time of coating of 1,000 to 10,000 mP.
a.s. Preferably, 2,000 to 9,000 mPa ·
s can be applied uniformly, stably, and at high speed. The viscosity at 25 ° C. is preferably 2,000 to 20,000 mPa · s. Preferably, 2,000 to 15,000 mPa · s, particularly, 2,000 to 9,000 mPa · s is effective.
The high-viscosity resin composition may be applied by heating the resin composition, keeping the resin composition at an appropriate viscosity.

[0122]

Next, the present invention will be described in more detail with reference to Examples, Comparative Examples and Production Examples. The diluent (B-1) used is summarized. As the monofunctional radically polymerizable unsaturated compound (B-1-1) having a cyclic structure, b1: isobornyl acrylate, b2: 8-hydroxymethyl-tricyclo “5.2.
2.0 ^2,6 "decane acrylate, b3: Alonix TO-1210: 1 ethylene oxide modified by Toagosei Co., Ltd., acrylate of dimethyl, phenyl substituted methylphenol b4: Aronix TO-1340: 1 propylene oxide modified dimethyl by Toagosei Co., Ltd. And an acrylate of phenyl-substituted methylphenol. Monofunctional radically polymerizable unsaturated compound having a nitrogen atom (B
-1-2), b5: N-vinylcaprolactam, b6: N-vinylpyrrolidone, b7: N-vinylformamide, b8: N-vinylacetamide, b9: N-vinylmethylacetamide, b10: acrylated morpholine, b11 : 1 Uses ethylene oxide-modified morpholine acrylate. As polyfunctional radical polymerizable unsaturated compounds (B-1-3), b12: tricyclodecane dimethanol diacrylate, b13: 4 ethylene oxide-modified bisphenol A diacrylate, b14: hydrogenated bisphenol A diacrylate, b15: penta Erythritol triacrylate is used.

As a monofunctional radically polymerizable unsaturated compound (B-1-4) having a homopolymer having a glass transition temperature of 20 ° C. or less, b16: nonylphenol ethylene oxide 1 mol-modified acrylate ｛Tg of homopolymer (hereinafter abbreviated as Tg) ) = 17 ° C., b17: 2-ethylhexyl-ethylene oxide 2 mol modified acrylate (Tg = −65 ° C., b18: nonylphenol ethylene oxide 4 mol modified acrylate (Tg = −20 ° C.), b19: nonylphenol propylene oxide average 2.5 Molar modified acrylate (Tg = −3 ° C.), b20: lauryl acrylate (Tg = −3 ° C.), b21: acrylate of butyl glycidyl ether (T
g = −12 ° C.), b22: 3 ethylene oxide-modified lauryl acrylate (Tg = −60 ° C.), b23: Alonix TO-1215 manufactured by Toagosei Co., Ltd. = branched alcohol acrylate having 18 carbon atoms (Tg = −40)
° C or less).

As the photopolymerization initiator (C-1), C1: 2,4,6-trimethylbenzoyldiphenylphosphine oxide; C2: Irgacure 819 manufactured by CSC; C3: 2-methyl-2-morpholino (4-methylthio) Phenyl) propan-1-one, C4: 1-hydroxycyclohexyl phenyl ketone, C5: 2,2-dimethoxy-1,2-diphenylethan-1-one, C6: 3,6-bis (2-methyl-2- Morpholinopropionyl) -9-n-octylcarbazole.

As antioxidants (C-4), C7: tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, C8: octadecyl-3- (3, 5-di-t-butyl-
4-hydroxyphenyl) propionate C9: bis [2-methyl-4-{3-n-alkyl (C ₁₂ or C ₁₄₎
Thiopropionyloxy} -5-t-butylphenyl] sulfide.

As the ultraviolet absorbent (C-5), C10: 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole is used.

As the light stabilizer (C-6), C11: bis (1,2,2,6,6-pentamethyl-4-piperidyl)
Sebacate C12: Adekastab LA-62 manufactured by Asahi Denka Co., Ltd. is used. As a coupling agent (C-14), C13: γ-mercaptopropyltrimethoxysilane,
Is used. As the silicone compound (C-16), C14: polydimethylsiloxane having a molecular weight of 500 and a polyoxyethylene / polyoxypropylene (75/25) copolymer having a molecular weight of 1500 are used.

Synthesis Example 1 In a flask equipped with a stirrer, a thermometer, and a reflux condenser, 800 g of polypropylene glycol having a number average molecular weight of 8000 was placed.
g (0.10 mol), 2,4-tolylene diisocyanate 3
4.6 g (0.20 mol) was charged, and the temperature was raised while stirring and maintained at 60 ° C. After 30 minutes at 60 ° C., 0.04 g of tin octylate (46 ppm in polyurethane) is added,
The reaction was further performed at 60 ° C. for 2 hours. Next, 0.09 g of t-butyl hydroquinone (103 pp in polyurethane)
m), 2-hydroxyethyl acrylate 11.9 (0.
103 mol) and 30.6 g (0.103 mol) of pentaerythritol triacrylate, and 0.04 g of tin octylate (46 ppm in polyurethane) was added. After reacting at 70 ° C. for 1 hour, 702 g of diluent (b16) was added, and the mixture was further reacted for 8 hours. Synthetic product 1: polymerizable polyurethane (A1) / (b16) having an average molecular weight of about 8,800 =
A 50/40 mixture was obtained.

Synthesis Example 2 In a flask equipped with a stirrer, thermometer and reflux condenser, 4000 g (2.0 mol) of a tetrahydrofuran-methyltetrahydrofuran copolymer having a number average molecular weight of 2,000, 2,4-
522 g (3.0 mol) of tolylene diisocyanate was charged, the temperature was raised while stirring, and the temperature was maintained at 60 ° C. After 30 minutes at 60 ° C., 0.25 g (50 ppm in polyurethane) of dibutyltin laurate was added, and the mixture was further reacted at 60 ° C. for 2 hours. Next, 0.50 g of t-butyl hydroquinone
148 g (1.03 mol) of 4-hydroxybutyl acrylate and 306 g (1.03 mol) of pentaerythritol triacrylate were charged, and 0.25 g of dibutyltin laurate (50 ppm in polyurethane) was added. After reacting at 70 ° C. for 1 hour, 1121 g of diluent (b17) and 1121 (b18)
g, and further reacted for 8 hours. Synthetic product 2: polymerizable polyurethane (A2) / (b1) having an average molecular weight of about 4,800
7) / (b18) = 50/20/20 mixture was obtained.

Synthesis Example 3 A flask equipped with a stirrer, thermometer and reflux condenser was charged with 4000 g (2 mol) of a modified ethylene oxide of butylene glycol having a number average molecular weight of 2000 and 504 g (3 mol) of hexamethylene diisocyanate. The temperature was raised while stirring and kept at 60 ° C. After 30 minutes at 60 ° C., 0.25 g of dibutyltin dilaurate (50% in polyurethane)
ppm) and reacted at 60 ° C. for 2 hours. Next, 0.50 g (100 ppm in polyurethane) of t-butyl hydroquinone, 134 g (1.03 mol) of 2-hydroxypropyl acrylate, and 380 g (1.03 mol) of diacrylate of trihydroxyethyl isocyanurate were charged. 0.25 g of tin (50 ppm in polyurethane) was added. After reacting at 70 ° C. for 1 hour, diluents (b19) (2007 g) and (b21) (2007 g) were added, and the mixture was further reacted for 8 hours. Synthetic product 3: average molecular weight 5,
000 polymerizable polyurethane (A3) / (b19) / (b
21) = 50/20/20 mixture was obtained.

Synthesis Example 4 In a flask equipped with a stirrer, a thermometer, and a reflux condenser, polybutylene glycol having a number average molecular weight of 3000 was added to 3000.
g (1.0 mol), 2,4-tolylene diisocyanate 34
8 g (2.0 mol) were charged, and the temperature was raised while stirring and the temperature was increased to 60 ° C.
Kept. After 30 minutes at 60 ° C., 0.19 g of dibutyltin laurate (50 ppm in polyurethane) was added, and the mixture was further reacted at 60 ° C. for 2 hours. Next, 0.09 g of t-butyl hydroquinone (103 pp in polyurethane)
m), 2-hydroxyethyl acrylate 119 (1.0
3 mol), pentaerythritol triacrylate 30
6 g (1.03 mol), and tin octylate 0.1
9 g (50 ppm in polyurethane) were added. The reaction was carried out at 70 ° C. for 9 hours to obtain a synthetic product 4: a polymerizable polyurethane (A4) having an average molecular weight of about 3,800.

Synthesis Example 5 Polypropylene glycol 1600 having a number average molecular weight of 8000 was placed in a flask equipped with a stirrer, a thermometer, and a reflux condenser.
0 g (2 mol), 666 g of isophorone diisocyanate
(3 mol), and the mixture was heated to 60 ° C. while stirring. After 30 minutes at 60 ° C., 0.86 g of dibutyltin dilaurate (50 ppm in polyurethane) was added, and the mixture was further reacted at 60 ° C. for 2 hours. Next, 1.72 g of t-butyl hydroquinone (100 ppm in polyurethane),
119 g (1.03 mol) of 2-hydroxyethyl acrylate and 380 g (1.03 mol) of diacrylate of trihydroxyethyl isocyanurate were charged, and 0.86 g of tin octylate (50 ppm in polyurethane) was added. After reacting at 70 ° C. for 1 hour, diluent (b19) 8583
g, (b22) 4291 g and (b23) 4291 g were added, and the mixture was further reacted for 8 hours. Synthetic product 5: average molecular weight 1
7,200 polymerizable polyurethanes (A5) / (b19) /
(B22) / (b23) = 40/20/10/10 mixture was obtained.

Synthesis Example 6 Polypropylene glycol 2000 having a number average molecular weight of 2000 was placed in a flask equipped with a stirrer, thermometer, and reflux condenser.
g (1.0 mol), 2,4-tolylene diisocyanate 34
8 g (2.0 mol) was charged and the temperature was increased while stirring.
C. After 30 minutes at 60 ° C, 0.14 g (50 ppm in polyurethane) of dibutyltin laurate was added, and the mixture was further reacted at 60 ° C for 2 hours. Next, 0.28 g of t-butyl hydroquinone (100 p in polyurethane)
pm) 119 g of 2-hydroxyethyl acrylate
(1.03 mol) and 306 g (1.03 mol) of pentaerythritol triacrylate were added, and 0.14 g (50 ppm in polyurethane) of dibutyltin laurate was added. After reacting at 70 ° C for 1 hour, 693 g of diluent (b1)
And further reacted for 8 hours. Synthetic product 6: polymerizable polyurethane (A6) / (b1) = 4 having an average molecular weight of about 2,800
A 0/10 mixture was obtained.

Synthesis Example 7 104 g of neopentyl glycol having a number average molecular weight of 104 was placed in a flask equipped with a stirrer, thermometer and reflux condenser.
(1.0 mol), 2,4-tolylene diisocyanate 348
g (2.0 mol), and the temperature was increased while stirring.
Kept. After 30 minutes at 60 ° C., 0.04 g of dibutyltin laurate (50 ppm in polyurethane) is added,
The reaction was further performed at 60 ° C. for 2 hours. Next, 0.08 g of t-butyl hydroquinone (100 pp in polyurethane)
m) 134 g of 2-hydroxypropyl acrylate
(1.03 mol) and 249 g (1.03 mol) of trimethylolpropane diacrylate were added, and 0.04 g of dibutyltin laurate (50 ppm in polyurethane) was added. After reacting at 70 ° C for 1 hour, 278 g of diluent (b2)
And further reacted for 8 hours. Synthetic product 7: polymerizable polyurethane having an average molecular weight of about 824 (A7) / (b2) = 30 /
Ten mixtures were obtained.

Synthesis Example 8 2000 g (1.0 mol) of propylene oxide-modified polytetramethylene glycol having a number average molecular weight of 2,000 and 444 g (2.0 mol) of isophorone diisocyanate were placed in a flask equipped with a stirrer, thermometer and reflux condenser. And heated to 60 ° C. while stirring. 60 ℃
After 30 minutes, 0.16 g (50 ppm in polyurethane) of dibutyltin laurate was added, and the mixture was further reacted at 60 ° C for 2 hours. Next, 0.32 g of t-butyl hydroquinone
(100 ppm in polyurethane), 433 g (1.03 mol) of polypropylene (6 mol) monoacrylate, 249 g of trimethylolpropane diacrylate
(1.03 mol) and 0.16 g of dibutyltin laurate (50 ppm in polyurethane) were added. 70
After 1 hour of reaction at ℃, 391 g of diluent (b1), (b3)
391 g was added, and the mixture was further reacted for 8 hours. Synthetic product 8: polymerizable polyurethane (A8) / (b) having an average molecular weight of about 3110
1) / (b2) = 40/5/5 mixture was obtained.

Synthesis Example 9 In a flask equipped with a stirrer, thermometer and reflux condenser, 2,000 g (1.0 mol) of a tetrahydrofuran-methyltetrahydrofuran copolymer having a number average molecular weight of 2,000 and 444 g (2.0 mol) of isophorone diisocyanate were placed. And heated to 60 ° C. while stirring. After 30 minutes at 60 ° C., 0.15 g (50 ppm in polyurethane) of dibutyltin laurate was added, and the mixture was further reacted at 60 ° C. for 2 hours. Next, t-butyl hydroquinone 0.31
g (100 ppm in polyurethane), ε-caprolactone (1 mol) modified hydroxyethyl monoacrylate 2
37 g (1.03 mol), 380 g (1.03 mol) of diacrylate of trihydroxyethyl isocyanurate
And 0.15 g of dibutyltin laurate (50 ppm in polyurethane) was added. After reacting at 70 ° C for 1 hour,
306 g of diluents (b1) and 306 g of (b4) were added, and the mixture was further reacted for 8 hours. Synthetic product 9: polymerizable polyurethane (A9) / (b1) / (b4) having an average molecular weight of about 3050 = 50
/ 5/5 mixture was obtained.

Synthesis Example 10 1000 g of propylene glycol having a number average molecular weight of 1,000 was placed in a flask equipped with a stirrer, a thermometer, and a reflux condenser.
(1.0 mol), 348 g of 4-tolylene diisocyanate
(2.0 mol), and the temperature was raised while stirring and maintained at 60 ° C. After 30 minutes at 60 ° C, 0.10 g (50 ppm in polyurethane) of dibutyltin laurate was added, and the mixture was further reacted at 60 ° C for 2 hours. Next, 0.20 g of t-butyl hydroquinone (100 pp in polyurethane)
m) 134 g of 2-hydroxypropyl acrylate
(1.03 mol), 540 g (1.03 mol) of dipentaerythritol heptaacrylate, and 0.10 g of dibutyltin laurate (50 pp in polyurethane).
m) was added. After reacting at 70 ° C for 1 hour, diluent (b3) 6
74 g and 337 g of (b12) were added and reacted for further 8 hours. Synthetic product 10: polymerizable polyurethane (A10) / (b3) / (b12) having an average molecular weight of about 2000 = 20 / 6.7.
/3.3 mixture was obtained.

Synthesis Example 11 A flask equipped with a stirrer, thermometer and reflux condenser was charged with 1000 g of Clapol 1010 having a number average molecular weight of 1,000.
(1.0 mol), 2,4-tolylene diisocyanate 348
g (2.0 mol), and the temperature was increased while stirring.
Kept. After 30 minutes at 60 ° C., 0.09 g of dibutyltin laurate (50 ppm in polyurethane) was added,
The reaction was further performed at 60 ° C. for 2 hours. Next, 0.18 g of t-butyl hydroquinone (100 pp in polyurethane)
m) 119 g of 2-hydroxyethyl acrylate
(1.03 mol) and 306 g (1.03 mol) of pentaerythritol triacrylate were added, and 0.09 g (50 ppm in polyurethane) of dibutyltin laurate was added. After reacting at 70 ° C. for 1 hour, diluent (b1) 443
g and (b13) 148 g were added, and the mixture was further reacted for 8 hours. Synthetic product 11: polymerizable polyurethane (A11) / (b1) / (b13) having an average molecular weight of about 1800 = 30 / 7.5.
/2.5 mixture was obtained.

Synthesis Example 12 Polytetramethylene glycol 10 having a number average molecular weight of 1,000 was placed in a flask equipped with a stirrer, a thermometer, and a reflux condenser.
Then, 00 g (1.0 mol) and 348 g (2.0 mol) of 2,4-tolylene diisocyanate were charged, and the temperature was raised while stirring and maintained at 60 ° C. After 30 minutes at 60 ° C., 0.09 g of dibutyltin laurate (50 ppm in polyurethane) was added, and the mixture was further reacted at 60 ° C. for 2 hours. Next, 0.18 g of t-butyl hydroquinone (10% in polyurethane)
0 ppm), 2-hydroxyethyl acrylate 119
g (1.03 mol) and 306 g (1.03 mol) of pentaerythritol triacrylate, and 0.09 g of dibutyltin laurate (50 ppm in polyurethane).
Was added. After reacting at 70 ° C. for 1 hour, diluent (b1) 443
g and (b14) 148 g, and further reacted for 8 hours. Synthetic product 12: polymerizable polyurethane having an average molecular weight of about 1800 (A12) / (b1) / (b14) = 30 / 7.5
/2.5 mixture was obtained.

Synthesis Example 13 A flask equipped with a stirrer, thermometer and reflux condenser was charged with 800 g of polypropylene glycol having a number average molecular weight of 8000.
g (0.10 mol), 2,4-tolylene diisocyanate 3
4.6 g (0.20 mol) was charged, and the temperature was raised while stirring and maintained at 60 ° C. After 30 minutes at 60 ° C., 0.04 g of tin octylate (46 ppm in polyurethane) is added,
The reaction was further performed at 60 ° C. for 2 hours. Next, 0.09 g of t-butyl hydroquinone (103 pp in polyurethane)
m), 2-hydroxyethyl acrylate 23.8 (0.
206 mol), and tin octylate 0.04 g
(46 ppm in polyurethane). After reacting at 70 ° C. for 1 hour, 687 g of diluent (b16) was added, and 8
The reaction was allowed to proceed for a period of time to obtain Synthetic product 13: a polymerizable polyurethane (B1) / (b16) = 50/40 mixture having an average molecular weight of about 8,600.

Synthesis Example 14 Polypropylene glycol 2000 having a number average molecular weight of 2000 was placed in a flask equipped with a stirrer, a thermometer and a reflux condenser.
g (1.0 mol), 2,4-tolylene diisocyanate 34
8 g (2.0 mol) was charged and the temperature was increased while stirring.
C. After 30 minutes at 60 ° C, 0.14 g (50 ppm in polyurethane) of dibutyltin laurate was added, and the mixture was further reacted at 60 ° C for 2 hours. Next, 0.28 g of t-butyl hydroquinone (100 p in polyurethane)
pm) 238 g of 2-hydroxyethyl acrylate
(2.06 mol), and 0.14 g (50 ppm in polyurethane) of dibutyltin laurate was added. 70
After reaction at 1 ° C. for 1 hour, 647 g of diluent (b1) was added, and the mixture was further reacted for 8 hours. Synthetic product 14: average molecular weight of about 2.5
80 polymerizable polyurethane (B2) / (b1) = 40/1
0 mixture was obtained.

Synthesis Example 15 Polypropylene glycol 2000 having a number average molecular weight of 2000 was placed in a flask equipped with a stirrer, a thermometer, and a reflux condenser.
g (1.0 mol), 2,4-tolylene diisocyanate 34
8 g (2.0 mol) was charged and the temperature was increased while stirring.
C. After 30 minutes at 60 ° C, 0.14 g (50 ppm in polyurethane) of dibutyltin laurate was added, and the mixture was further reacted at 60 ° C for 2 hours. Next, 0.28 g of t-butyl hydroquinone (100 p in polyurethane)
pm), pentaerythritol triacrylate 612
g (2.06 mol) and 0.14 g (50 ppm in polyurethane) of dibutyltin laurate were added. 70
After reacting at 1 ° C. for 1 hour, 740 g of diluent (b1) was added, and the mixture was further reacted for 8 hours.
50 polymerizable polyurethane (B3) / (b1) = 40/1
0 mixture was obtained.

Synthesis Example 16 791 g (6.09 mol) of 2-hydroxypropyl acrylate and 174 g (1.0 g) of 2,4-tolylene diisocyanate were placed in a flask equipped with a stirrer, thermometer and reflux condenser.
Mol) and 0.13 g (100 ppm in polyurethane) of t-butylhydroquinone, and the temperature was raised while stirring and maintained at 55 ° C. One hour later, 174 g (1.0 mol) of 2,4-tolylene diisocyanate was added, and at 70 ° C,
The reaction was performed for 1.5 hours. After cooling to 60 ° C., 174 g (1.0 mol) of 2,4-tolylene diisocyanate was added. 7
After reaction at 0 ° C for 1 hour, 0.11 g of dibutyltin laurate
(80 ppm in polyurethane), and at 70 ° C.,
The reaction was carried out for 10 hours to obtain a synthetic product 16: a polymerizable polyurethane (B4) having an average molecular weight of about 434.

Synthesis Example 17 A flask equipped with a stirrer, thermometer and reflux condenser was charged with 400 g (1.0 mol) of ethylene oxide 4 mol-added bisphenol A having a number average molecular weight of 400 and 348 g (2,4-tolylene diisocyanate). .0.0 mol), and the mixture was heated while stirring and kept at 60 ° C. After 30 minutes at 60 ° C, 0.05 g of dibutyltin laurate (50% in polyurethane)
ppm) and reacted at 60 ° C. for 2 hours.
Next, 0.10 g (100 ppm in polyurethane) of t-butyl hydroquinone and 239 g (2.06 mol) of hydroxyethyl acrylate were charged, and 0.05 g of dibutyltin laurate (50 ppm in polyurethane) was added. After reacting at 70 ° C. for 1 hour, 247 g of diluent (b1) was added, and the mixture was further reacted for 8 hours. Synthetic product 17: polymerizable polyurethane (B5) having an average molecular weight of about 980 / (b1) = 40 /
Ten mixtures were obtained.

Synthesis Example 18 In a flask equipped with a stirrer, thermometer and reflux condenser, 484 g of epoxy acrylate having a number average molecular weight of 484 (1.
0 mol), 174 g of 2,4-tolylene diisocyanate
(1.0 mol), and the temperature was raised while stirring and maintained at 60 ° C. After 30 minutes at 60 ° C., 0.04 g of dibutyltin laurate (50 ppm in polyurethane) was added, and the mixture was further reacted at 60 ° C. for 2 hours. Next, 0.08 g of t-butyl hydroquinone (100 pp in polyurethane)
m), 119 g of hydroxyethyl acrylate (1.0 g
3 mol) and 0.04 g of dibutyltin laurate
(50 ppm in polyurethane). After reacting at 70 ° C. for 1 hour, 194 g of diluent (b1) was added and the mixture was further reacted for 8 hours to obtain a synthetic product 18: a polymerizable polyurethane (B6) / (b1) = 40/10 mixture having an average molecular weight of about 780. . The following Examples and Comparative Examples are described using synthetic products A1 to A12 and B1 to B6.

Example 1 In a container equipped with a stirrer, synthetic product 1: asymmetric polymerizable linear polyurethane (A-1) 50 / diluent (B16) = 50/40
, 90 parts of (b5) and 2 parts of the photoinitiator (C1) were mixed with stirring at 50 to 70 ° C. to obtain a resin composition (1).

Examples 2 to 12 and Comparative Examples 1 to 3 Resin compositions (2) to (12) were obtained in the same manner as in Example 1. Table 1 summarizes the results.

Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Resin composition (1) (2) (3) (4) (5) (A) A1: 50 A2: 50 A3: 50 A4: 85 A5: 40 (B-1) b16: 40 b17: 20 b19: 20 b20: 5 b19: 20 b18: 20 b21: 20 b22: 10 b23: 10 b5: 10 b5: 5 b8: 10 b5: 10 b6: 10 b7: 5 b15: 5 (C) C1: 2 C2: 1 C6: 1 C3: 1 C1: 2 C4: 1 Total 102 101 101 102 102 102 Example 6 Example 7 Example 8 Example 9 Example 9 10 Resin composition (6) (7) (8) (9) (10) (A) A6: 40 A7: 30 A8: 40 A9: 50 A10: 20 A640 A6: 10 (B-1) b1: 15 b1: 20 b1: 10 b1: 15 b1: 10 b2: 1 b4: 5 b3: 6.7 b16: 20 b12: 3.3 b5: 15 b6: 5 b6: 5 b5: 10 b6: 10 b10: 5 b11: 10 (B-2) B4: 30 B6: 20 B5: 40 (C) C3: 1 C3: 1 C1: 2 C2: 1 C6: 1 C4: 1 C5: 1 Total 102 102 102 101 101 Example 11 Example 12 Comparative Example 1 Comparative Example 2 Comparative Example 3 Resin composition (11) (12) (13) (14) (15) (A) A11: 30 A12: 30 (B-1) b1: 32.5 b1: 17.5 b16: 40 b1: 15 b1: 15 b13: 2.5 b14: 2.5 b5: 15 b6: 5 b5: 10 b5: 15 b5: 15 b15: 5 (B-2) B4: 10 B4: 40 B1: 50 B2: 40 B3: 40 B6: 10 B4: 30 B4: 30 (C) C3: 1 C3: 1 C1: 2 C3: 1 C3 : 1 C4: 1 C5 1 C4: 1 C4: 1 Total 102 102 102 102 102

For the resin compositions (1) to (15), the viscosity and the irradiation amount were 200 mJ / cm by the method described below.
The tensile modulus, tensile elongation at break, curability, and low-temperature stability in Example ² were measured, and the measurement results and judgment are shown in Table 2.

(Viscosity) Based on JIS K7117, B
No. was measured by a viscometer. 4 rotors, 60 rpm
At 25 ± 0.5 ° C. (unit: mPa · s)
Was measured. 2000 to 9,000 mPa · s is good:
(○), 9,000 to 15,000 mPa · s is slightly better: (△) (available if heated to high temperature during coating), less than 2,000 mPa · s and 15,000 m
Not more than Pa · s: judged as (x).

(Tensile Elastic Modulus) A resin composition was coated on a glass plate to a thickness of 200 ± 50 μm,
200mJ / with 120W / cm metal halide lamp
cm ^{2 was} irradiated to obtain a cured coating film. This coating is released and J
According to IS K-7113, under the conditions of 23 ° C and 50% RH,
A 2.5% secant elastic modulus at a tensile speed of 1 mm / min and a mark line of 25 mm was measured and defined as a tensile elastic modulus (kg / mm ² ).

(Tensile Elongation at Break) The resin composition was coated on a glass plate to a thickness of 200 ± 50 μm, and
200mJ / with 120W / cm metal halide lamp
cm ^{2 was} irradiated to obtain a cured coating film. This coating is released and J
According to IS K-7113, under the conditions of 23 ° C and 50% RH,
Tensile breaking elongation (%) was measured at a tensile speed of 50 mm / min and a mark line of 25 mm. Good tensile elongation at break of 40% or more:
(○), 35% to 40% slightly better: (△) (when used for two-layer coating, it can be used if the tensile modulus of the other coating layer is effective) No less than 35%:
(X).

(Curability) In the above-described method for measuring the tensile modulus, the film thickness was set to 40 ± 10 μm and the irradiation amount was set to 25 mJ.
/ Cm ² , 500 mJ / cm ² , a coating film was prepared, tensile modulus was measured, E25 and E500 were obtained, and curability (%) = (E25 / E500) × 100 was calculated.

Optical fiber production line (line speed:
The irradiation dose of 1800 m / min) corresponds to 25 mJ / cm ² . For a coating film with a tensile modulus of 0.05 to 1 kg / mm2,
90% or more: good (（), less than 90%: bad
(X) was determined. Tensile modulus of elasticity 1 to 200 kg / mm2
80% or more is good: (○)
% Is not acceptable: determined as (x).

(Low-temperature stability) The resin composition was left at 0 ° C. for one month, and the form was observed. Good things that don't change:
Good (を) and cloudy (return to transparent liquid after standing at 40 ° C. for less than 6 hours): Poor (△) and cloudy (no return to clear liquid after leaving at 40 ° C. for 6 hours)
Not possible: (x).

Table 2 Example 1 Example 2 Example 3 Example 4 Example 5 Resin composition (1) (2) (3) (4) (5) Viscosity 4500: 5200: 3900: 12000: △ 6000: ○ Tensile modulus 0.12 0.22 0.36 0.82 0.06 Tensile elongation at break 220: ○ 180: ○ 190: ○ 110: ○ 200: ○ Curability 96: ○ 94: ○ 93: ○ 94: ○ 91: ○ Low temperature stability ○ ○ ○ ○ ○ Example 6 Example 7 Example 8 Example 9 Example 10 Resin composition (6) (7) (8) (9) (10) Viscosity 3500: ○ 8100: ○ 5000: ○ 6800: ○ 4800 ： ○ Tensile modulus 85 50 30 5 160 Tensile fracture elongation 40 ： ○ 50 ： ○ 80 ： ○ 100 ： ○ 35 ： △ Curability 86 ： ○ 81 ： ○ 80 ： ○ 90 ： ○ 85 ： ○ Low temperature stability ○ ○ ○ ○ ○ Example 11 Example 12 Comparative Example 1 Comparative Example 2 Comparative Example 3 Resin composition (11) (12) (13) (14) (15) Viscosity (mPa · s) 10000: △ 6200: ○ 4300: ○ 3300: ○ 4200 ○ Tensile modulus 50 120 0.11 70 160 Tensile breaking elongation 50: ○ 40: ○ 220: ○ 40: ○ 30: × Curability 85: ○ 84: ○ 85: ** 75: × 86: ○ Low temperature stability △ ○ ○ ＊ * The tensile elasticity is 0.05 to 1 kg / mm2, and the curability is not 85%.

Example 13 In a container equipped with a stirrer, 102 parts of the resin composition (1),
Antioxidant (C9): 0.5 part, coupling agent (C1
3): 0.1 part was charged and stirred and mixed at 50 to 70 ° C. to obtain a resin composition (16).

Example 14 A container equipped with a stirrer was charged with 102 parts of the resin composition (6).
Antioxidant (C7): 0.5 part, light stabilizer (C11):
0.5 part was charged and stirred and mixed at 50 to 70 ° C. to obtain a resin composition (17).

Example 15 In a container equipped with a stirrer, 102 parts of the resin composition (6),
Antioxidant (C7): 0.5 part, light stabilizer (C11):
0.5 parts, pigment paste (phthalocyanine / diluent (b
13) = 50/50 which was minced with three rolls) 5
Parts, and stirred and mixed at 50 to 70 ° C. to obtain a resin composition (1).
8) was obtained.

Example 16 In a container equipped with a stirrer, 102 parts of the resin composition (6),
Antioxidant (C8): 0.5 part, ultraviolet absorber (1
0): 0.5 part, a light stabilizer (C12): 0.5 part, and a silicone compound (C14): 3 parts were charged and stirred and mixed at 50 to 70 ° C. to obtain a resin composition (19).

With respect to the resin compositions (16) to (19),
The aging characteristics and the amount of generated hydrogen were measured by the methods described below. Table 3 summarizes the results.

(Aging Characteristics) A resin composition was placed on a glass plate at a predetermined thickness ｛resin compositions (16), (17),
(19) is 200 ± 50 μm resin composition (18)
Was coated at 8 ± 1 μm１, and irradiated with 200 mJ / cm ^{2 from} a 120 W / cm metal halide lamp under a nitrogen atmosphere to obtain a cured coating film. This coating film is liberated (hereinafter referred to as “releasing coating film”), and 23 ° C. 50% RH according to JIS K-7113.
Under the condition of 1 mm / min at a pulling speed of 25 mm between the marked lines
Measure the 2.5% secant modulus and determine the tensile modulus (kg / m
m ² ), the tensile breaking elongation (%) and the tensile breaking strength (kg / mm 2) at a distance of 25 mm between the marked lines were measured at a tensile speed of 50 mm / min, and were used as initial values. Next, the free coating film is placed in the air at 80
The sample was left for 30 days at 80 ° C for 30 days in warm water. Tensile modulus of the free coating film after standing (kg / m
m ² ), tensile elongation at break (%), tensile strength at break (kg / m
m2) was measured, and the ratio to the initial value was determined.
(Value after standing / initial value) × 100 was calculated. Good: (○) when the retention was ± 50% or more.

(Hydrogen generation amount) A free coating film was prepared under the same conditions as the aging characteristics, put in an appropriate amount in a headspace bottle, heated at 100 ° C. for 24 hours, allowed to cool, and the gas in the bottle was collected. The amount of generated hydrogen is quantified by a gas chromatography method. 1 μL / g or less was evaluated as good: (○).

Table 3 Example 13 Example 14 Example 15 Example 16 Resin composition (16) (17) (18) (19) Viscosity (mPa · s) 4500: ○ 3500: ○ 4000: ○ 3400: ○ <Initial value> Tensile modulus 0.12 85 100 85 Tensile breaking elongation 220: ○ 40: ○ 40: ○ 40: ○ Tensile breaking strength 0.50 4.2 4.2 4.2 <Degradation with time> (Air Medium) Tensile modulus 102: ○ 103: ○ 102: ○ 102: ○ Tensile breaking elongation 96: ○ 97: ○ 97: ○ 97: ○ Tensile breaking strength 103: ○ 103: ○ 104: ○ 102: ○ (Warm water ) Tensile modulus 99 :： 98: ○ 99: ○ 98: ○ Tensile breaking elongation 94: ○ 95: ○ 94: ○ 95: ○ Tensile breaking strength 99: ○ 98: ○ 97: ○ 99: ○ Hydrogen generation amount 0 .5 0.1 0.1 0.1 0.1

Regarding the resin compositions (16) to (19),
The adhesion between the layers was measured by the method described below.

(Adhesion between layers) The resin composition (16) was applied to a glass substrate having a cleaned surface at a thickness of 200 ± 50 μm, and was coated with a metal halide lamp of 120 W / cm in a nitrogen atmosphere at a rate of 200 mJ / cm. Irradiation was performed ² to obtain a cured coating film A. A 180 degree peel test was performed at a pulling speed of 200 mm / min, and the adhesion was measured. 10-50g / 10mm
Is good: (○). The evaluation result is 15 g / 10 mm:
(○).

On the cured coating film A, the resin composition (17)
Is applied to a thickness of 50 ± 5 μm, and under a nitrogen atmosphere, 120 W
200mJ / cm ^{2 with} a metal halide lamp of
Irradiation gave cured coating B. The adhesion between the cured coating film A and the cured coating film B was evaluated by a cross-cut method. The case where it was not peeled off was evaluated as good: (（). The evaluation result does not peel:
(○).

On the cured coating film B, the resin composition (18)
Is applied to a thickness of 8 ± 1 μm, and in a nitrogen atmosphere, 120 W / c
Irradiation was performed with a 200 mJ / cm ² metal halide lamp to obtain a cured coating film C. The adhesion between the cured coating film B and the cured coating film C was evaluated by a cross-cut method. The case where it does not peel off is regarded as good. The evaluation result was not peeling: (○).

On the cured coating film C, a resin composition (19)
Is coated to a thickness of 200 ± 50 μm, and under a nitrogen atmosphere,
200mJ / with 120W / cm metal halide lamp
cm ^{2 was} irradiated to obtain a cured coating film D. Pulling speed 200mm
At 180 ° C./min, a 180 ° peel test was performed to measure the adhesion. Good: 10 to 30 g / mm: (Good). The evaluation result was 18 g / 10 mm: (○).

For the resin compositions (16) to (19),
The optical fiber characteristics were evaluated by the method described below.

(Optical Fiber Characteristics) A resin composition (1) was used as a primary material in a 125 μm-diameter SM optical fiber.
6) As a secondary material, a resin composition (17) was coated to prepare an optical fiber core wire having a diameter of 250 μm. The transmission loss of the optical fiber core is 1.55 μm and 0.18 dB.
/ Km.

The above-mentioned optical fiber having a diameter of 250 μm is
As an ink, the resin composition (18) was applied to a thickness of 8 ± 1 μm to prepare an optical fiber colored core. The transmission loss of the colored optical fiber is 1.55 μm and 0.18 dB /
km.

The four colored cords were used as a collective material, and a resin composition (19) was used to form a four-core cord.
The transmission loss of the optical fiber colored core of the tape core is 1.5.
It was 0.18 dB / km at 5 μm. The transmission loss after immersion in warm water at 60 ° C. for 30 days was 0.30 dB / km.

[0174]

The resin composition for coating an optical fiber according to the present invention is suitable for high-speed processing required at present, and has high curability which sufficiently cures at a low irradiation dose. At the same time, it is an optical fiber coating resin composition having excellent toughness that satisfies the mechanical properties and durability required for a core wire, a colored core wire, a unit, and an overcoated core wire. As a result,
By using the resin composition of the present invention, optical fibers, colored cores, units, and overcoated cores excellent in mechanical properties and durability can be mass-produced in a short time.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Naoto Kojiro 84-1 Oshikiya, Oji, Ageo-shi, Saitama 3-16-408 Nishiageo F-term (reference) 2H050 BB14W BB33W BB34W BD02 4G060 AC15 AD22 CB22 4J038 FA011 FA012 FA041 FA042 FA061 FA062 FA101 FA102 FA121 FA122 FA131 FA132 FA141 FA142 FA151 FA152 FA171 FA172 FA281 FA282 KA03 MA14 NA11 PA17 PB08 PC08

Claims (7)

[Claims] An optical fiber coating comprising an asymmetrically polymerizable linear polyurethane compound (A) having two or more radically polymerizable groups at one end and one radically polymerizable group at the other end. Resin composition. 2. The asymmetric polymerizable linear polyurethane compound (A) has two or three radical polymerizable groups at one end.
2. The resin composition according to claim 1, which is an asymmetrically polymerizable linear polyurethane compound having one and one radically polymerizable group at the other end. 3. Asymmetrically polymerizable linear polyurethane (A)
Is a polyether diol polyurethane.
Or the resin composition according to 2. 4. Asymmetrically polymerizable linear polyurethane (A)
Is a polyether diol polyurethane having a side chain. 5. The resin composition according to claim 1, wherein the asymmetrically polymerizable linear polyurethane compound (A) has a number average molecular weight of 500 to 20,000. 6. The cured product of the resin composition has a tensile modulus of elasticity
When it is 0.05 to 1 kg / mm ² , the number average molecular weight is 3,
The asymmetric polymerizable linear polyurethane compound (A) having a content of 500 to 20,000 was added in an amount of 35 to 95 parts based on 100 parts of the sum of (A) and the other polymerizable unsaturated compound (B). The tensile modulus of the cured product is 1 to 200 kg / mm
^{When 2} , the asymmetric polymerizable linear polyurethane compound having a number average molecular weight of 500 to 3,500 (A) is
Sum of (A) and other polymerizable unsaturated compound (B) 10
2. The method according to claim 1, wherein the content is 20 to 80 parts per 0 parts.
The resin composition according to any one of claims 1 to 5, wherein 7. An optical fiber core, a colored core, a unit or an overcoat core coated with a cured product of the resin composition according to any one of claims 1 to 6.