JP2610491B2 - Liquid curable resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a liquid curable resin composition, and more specifically, a liquid curable resin composition suitable as a hard material for an optical fiber or a bundling material for a tape-shaped fiber. About things.

[Conventional technology]

In the production of an optical fiber, a resin coating is applied immediately after the hot melt spinning of the glass fiber for the purpose of protection and reinforcement.

As the resin coating, a flexible primary coating layer is first provided on the surface of the optical fiber, and a second layer having a higher rigidity is provided on the outer side thereof.
The structure provided with the following coating layer is well known. Also, a tape-shaped fiber in which several resin-coated optical fibers are arranged and further resin-coated and fixed is well known.

The resin composition for forming the primary coating layer is a soft material, the resin composition for forming the secondary coating layer is a hard material, and the resin composition for fixing a plurality of optical fibers. Things are called bundling materials.

As these resin coating methods, a method of applying a liquid resin composition and curing it with heat or light, particularly ultraviolet light, is often used.

In recent years, there has been an increasing demand for higher drawing speeds of optical fibers, and a higher demand for hardening speeds for hard materials or bundling materials than ever before.

Polyether-based urethane acrylates have the advantage that the curing rate is higher than other polyester-based, polyolefin-based or polycarbonate-based systems.However, the viscosity of the polyether-based urethane acrylate alone is too high, and the Young's modulus of the obtained cured product is low. It is not suitable as a hard material or bundling material for optical fibers.

Therefore, conventionally, the viscosity has been reduced by mixing a reactive diluent with a polyether-based urethane acrylate. However, if a large amount of a vinyl monomer such as vinylpyrrolidone or vinylcaprolactam is added as a reactive diluent in order to obtain a desired curing rate, the resulting cured product will have an excessively high water absorption and will not be suitable as a hard material or a bundling material. In addition, if a trifunctional or higher polyfunctional acrylic monomer is mixed as a reactive diluent, the curing speed increases, and the Young's modulus of the cured product also increases. The toughness of the object is impaired.

[Problems to be solved by the invention]

An object of the present invention is to provide a composition suitable as a hard material or a bundling material for an optical fiber having a low viscosity, a high curing speed, and a high toughness, particularly as a hard material or a bundling material.

[Means for solving the problem]

The present invention solves the above-mentioned problems. (A) Urethane (meth) acrylate having a polyoxyalkylene structure 14 to 70% by weight (b) Urethane (meth) having a tricyclodecane structure
The present invention provides a liquid curable resin composition comprising 5 to 40% by weight of an acrylate, (c) a reactive diluent, and (d) a polymerization initiator.

Urethane (meth) acrylate having a polyoxyalkylene structure, which is component (a) of the composition of the present invention (hereinafter, referred to as "urethane (meth) acrylate (a)").
Is obtained by reacting a diol having a polyoxyalkylene structure, a polyisocyanate, and a (meth) acrylate compound having a hydroxyl group.

The following urethane (meth) acrylate (a)
The following is an example of the production method.

[Production Method 1] A method of reacting a hydroxyl group-containing (meth) acrylate with an isocyanate group of an intermediate obtained by reacting a diol having a polyoxyalkylene structure with diisocyanate.

[Production Method 2] A method in which a diol having a polyoxyalkylene structure is reacted with an isocyanate group of an adduct obtained by reacting a diisocyanate with a (meth) acrylate having a hydroxyl group.

[Production Method 3] A method of simultaneously reacting a diisocyanate, a diol having a polyoxyalkylene structure, and a (meth) acrylate having a hydroxyl group.

[Production Method 4] A method in which a compound having a (meth) acryloyl group and an isocyanate group in one molecule is reacted with a diol having a polyoxyalkylene structure.

Examples of the diol having a polyoxyalkylene structure used in the above production methods 1 to 4 include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol, polydecamethylene glycol, two or more ions. Examples thereof include polyether diols obtained by ring-opening copolymerization of a polymerizable cyclic compound.

Here, as the ion-polymerizable cyclic compound, ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, dioxane, trioxane, tetraoxane, 3-methyltetrahydrofuran,
2-methyltetrahydrofuran, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl silohexene oxide, phenyl glycidyl ether And cyclic ethers such as butyl glycidyl ether and glycidyl benzoate.

Further, the above-mentioned ion-polymerizable cyclic compound was subjected to ring-opening copolymerization with a cyclic imine such as ethyleneimine, a cyclic lactone such as p-propiolactone, glycolic lactide or a cyclic siloxane such as dimethylcyclopolysiloxane. Polyether diols can also be used.

Specific examples of the combination of two or more ion-polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, and 3-methyltetrahydrofuran and tetrahydrofuran.

Further, the open-ring polymer of two or more ion-polymerizable cyclic compounds may be bonded at random.

Further, as the diol having a polyoxyalkylene structure, the diol having a polyoxyalkylene structure is reacted with a dibasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid. The obtained polyester diol, polycaprolactone diol obtained by reacting the diol having a polyoxyalkylene structure with ε-caprolactone, and the like can also be used.

Diols having these polyoxyalkylene structures include, for example, PTMG1000 (Mitsubishi Kasei Kogyo), PTMG2000
(Same), PPG1000 (Asahi Orin Co., Ltd.); PPG2000
(Same), EXCENOL2020 (same), EXCENOL1020 (same), PEG1
000 (Nippon Oil & Fats Co., Ltd.), Unisafe DC1100 (same), Unisafe DC1800 (same), PPTG2000 (Hodogaya Chemical), PP
TG1000 (same), PTG400 (same), PTG3000 (same), PTGL200
It can also be obtained as commercial products such as 0 (same) and PTGL3000 (same).

The diol having no polyoxyalkylene structure may be used in combination with the diol having no polyoxyalkylene structure.

Examples of the diol having no polyoxyalkylene structure include low-molecular-weight diols such as ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and spiro glycol.
Polyester diol, ethylene glycol, tetramethylene glycol, 1,6 obtained by reacting the low molecular weight diol with a dibasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid. Polycaprolactone diol obtained by reacting diols such as hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,4-butanediol with DN-980 (Nippon Polyurethane Co., Ltd.), DN-981 (Same), DN-982 (same), DN-983
And diols such as PC-8000 (US PPG).

Examples of the diamine include ethylenediamine, tetramethylenediamine, hexamethylenediamine, para-phenylenediamine, 4,4'-diaminodiphenylmethane, a diamine containing a hetero atom, and a diamine having a polyoxyalkylene structure.

As the diisocyanate used in the above production methods 1 to 3, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate,
1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p
Phenylenediisocyanate, 3,3'-dimethyl-4,
4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate,
2,2,4-trimethylhexamethylene diisocyanate,
Bis (2-isocyanateethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate and the like can be mentioned.

Having a hydroxyl group (meth) used in the above production methods 1 to 3
Examples of the acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and trimethylolpropane. Di (meth) acrylate, trimethylolethanedi (meth) acrylate,
Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 1,4
-Butanediol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerin di (meth) acrylate, represented by the following formula (Meth) acrylates, and compounds obtained by an addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, aryl glycidyl ether, glycidyl (meth) acrylate, and (meth) acrylic acid.

(In the formula, R ¹ is H or CH ₃ , and n is 1 to 5.) The compound having a (meth) acryloyl group and an isocyanate group in one molecule used in the above production method 4 is represented by the following formula. Compounds.

(Wherein R ¹ is H or CH ₃ ).

The amount of the diisocyanate used per equivalent of the hydroxyl group of the diol having a polyoxyalkylene structure is about 0.5 to
2 moles. In this reaction, the reaction is usually performed using a catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, n-butyltin laurate, and triethylamine in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total amount of the reaction raw materials. . The reaction temperature in this reaction is usually 0 to 80 ° C.

The amount of the (meth) acrylate having a hydroxyl group based on the isocyanate group of the intermediate thus obtained is about 1 mol per 1 equivalent of the isocyanate group of the intermediate, and the reaction conditions are as follows. Are the same as the reaction conditions in the synthesis of the intermediate.

 Next, an embodiment of the above-mentioned production method 2 will be described.

A diol having a polyoxyalkylene structure is reacted with 0.5 to 2 moles of a (meth) acrylate having a hydroxyl group per 1 mole of diisocyanate under the same reaction conditions as in Production Method 1 for 1 equivalent of an isocyanate group of an adduct. The reaction is carried out under the same reaction conditions as in Production Method 1, using the hydroxyl groups in an amount of about 1 equivalent.

 Next, an embodiment of the above-mentioned production method 3 will be described.

The amount of the diisocyanate used per equivalent of the hydroxyl group of the diol having a polyoxyalkylene structure is 0.5 to 2 mol.

The amount of the (meth) acrylate having a hydroxyl group is selected such that the total amount of the hydroxyl group with the hydroxyl group of the diol having a polyoxyalkylene structure is 0.9 to 1.1 times the amount of the isocyanate group of the diisocyanate.

However, in the production methods 1 and 2, when a (meth) acrylate compound having two or more hydroxyl groups in one molecule is used, the amount of the (meth) acrylate compound having a hydroxyl group is determined based on the number of hydroxyl groups in one molecule. It is necessary to use the amount divided by the amount.

 Next, an embodiment of the above-mentioned production method 4 will be described.

The amount of the compound having a (meth) acryloyl group and an isocyanate group in one molecule is selected so that the amount of the isocyanate group is 0.9 to 1.1 times the amount of the hydroxyl group of the diol having a polyoxyalkylene structure.

In performing the above production methods 1 to 3, when a part of the diol having a polyoxyalkylene structure is replaced with a diol or a diamine having no polyoxyalkylene structure and used in combination, a diol having a polyoxyalkylene structure, About 0.5 to 2 moles of diisocyanate is used per equivalent of the sum of hydroxyl groups and amino groups of diols and diamines having no alkylene structure.

Furthermore, when carrying out the above-mentioned production methods 1 to 3, the product gels with a polyol other than difunctional to diol, a polyamine other than difunctional to diamine or a polyisocyanate other than difunctional to diisocyanate. They can be used together to such an extent that they are not used. Usually, the used amount is 5 to 30 parts by weight based on 100 parts by weight of diol, diamine or diisocyanate. Examples of the non-bifunctional polyol herein include, for example, an addition product of glycerin and propylene oxide, glycerin, 1,2,3-pentanetriol, 1,2,3-butanetriol, and tri (2-hydroxypolyoxypropyl) polyol. Examples thereof include siloxane, polycaprolactone triol, polycaprolactone tetraol, liquid polybutadiene having more than two hydroxyl groups in one molecule, and hydrogenated products thereof.
Examples of the non-bifunctional polyamine include, for example, diethylene triamine, 1,2,3-triaminopropane, and polyoxypropylene amine.Examples of the non-bifunctional polyisocyanate include polymethylene polyphenyl isocyanate, triphenyl Methane 4,4 ', 4 ″
-Triisocyanate and the like.

In the present invention, the urethane (meth) acrylate (a) contains an ethylenically unsaturated group usually at 0.8 to 8% by weight, preferably 1 to 5% by weight, and has a number average molecular weight of 1,000 to 7000. Is preferable, and the range of 1500 to 5000 is particularly preferable. When the number average molecular weight of the urethane (meth) acrylate (a) is less than 1,000, the elongation at break of the cured product of the obtained composition decreases, the toughness is easily reduced, and the Young's modulus at a low temperature is easily increased. If it exceeds 7000, the viscosity of the composition becomes high and it becomes difficult to handle. Also, urethane (meth) acrylate (a)
The proportion of the polyoxyalkylene structure in the polymer is preferably from 50 to 98% by weight, particularly preferably from 60 to 93% by weight, and most preferably from 70 to 90% by weight. If the proportion of the polyoxyalkylene structure in the urethane (meth) acrylate (a) is less than 50% by weight, the Young's modulus of the cured product at a low temperature tends to increase, and it is transmitted when used as a coating material for an optical fiber. It is easy to cause loss.

The polyoxyalkylene structure in the urethane (meth) acrylate (a) is particularly preferably a polyoxytetramethylene structure. Accordingly, as the diol used for producing the urethane (meth) acrylate (a), polytetramethylene glycol and a copolymerized diol of tetrahydrofuran and 3-methyltetrahydrofuran are preferable.

Similarly, as the diisocyanate, 2,4-tolylene diisocyanate, isophone diisocyanate, hydrogenated bisphenol A diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate are preferable, and isophorone diisocyanate is particularly preferable.

Similarly, as the (meth) acrylate having a hydroxyl group, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or an acrylate represented by the following formula is preferable.

(Wherein, R ¹ is H or CH ₃ , and n is 1 to 5) The urethane (meth) acrylate (a) described above
Is preferably added to the composition of the present invention in the range of 14 to 70% by weight, particularly 16 to 60% by weight. Urethane (meta)
When the proportion of the acrylate (a) is less than 14% by weight, the elongation at break of the cured product of the obtained composition decreases, and when it exceeds 70% by weight, the Young's modulus of the cured product near room temperature decreases and the composition becomes Viscosity increases, and the handleability tends to deteriorate.

The urethane (meth) acrylate having a tricyclodecane structure (hereinafter, referred to as "urethane (meth) acrylate (b)"), which is the component (b) of the composition of the present invention, includes a urethane (meth) acrylate (a )), The diol having a polyoxyalkylene structure may be replaced with the diol having a tricyclodecane structure in the above-described manufacturing methods 1 to 4.

Examples of the diol having a tricyclodecane structure used in the above method include tricyclodecane diol, tricyclodecane dialcohol such as tricyclodecane diethanol, ε-caprolactone adduct diol of tricyclodecane dialcohol, and tricyclodecane diol. (Poly) alkylene oxide adduct diols of alcohols and the like can be mentioned.

In addition, it has a diisocyanate and a hydroxyl group (meth)
Examples of the acrylate include those similar to those used in the production of the urethane (meth) acrylate (a).

As an embodiment of the urethane (meth) acrylate (b), the urethane (meth) acrylate (a)
In the production methods 1 to 4, the diol having a polyoxyalkylene structure may be replaced with a diol having a tricyclodecane structure.

In producing the urethane (meth) acrylate (b), a part of the diol having a tricyclodecane structure can be replaced with a diol represented by the following formula.

HOR ² O _x R ³ OR ⁴ _y OH (wherein R ² and R ⁴ may be the same or different, and CH _2
2 or And R ³ is Where x and y are average values, each of which is 0.1 ≦ x
≦ 15 and 0.1 ≦ y ≦ 15) The urethane (meth) acrylate (b) contains an ethylenically unsaturated group in an amount of usually 1.3 to 11% by weight, preferably 2 to 7% by weight.
% By weight and has a number average molecular weight of 500
It is preferably from 1000 to 1000, and particularly preferably from 700 to 900. If the number average molecular weight of the urethane (meth) acrylate (b) is less than 500, the solubility in the reactive diluent (c) described later will be poor, and the number average molecular weight of the urethane (meth) acrylate (b) will be low. If it exceeds 1,000, the viscosity of the composition increases and the handleability deteriorates. The proportion of the tricyclodecane structure in the urethane (meth) acrylate (b) is preferably 15% by weight or more, and more preferably 20% by weight or more. If the proportion of the structure in the urethane (meth) acrylate (b) is less than 15% by weight, the toughness of the obtained cured product is impaired.

As the diol having a tricyclodecane structure, tricyclodecane dimethanol is most preferred. Preferred examples of the compound having a diisocyanate and a hydroxyl group are the same as those of the urethane (meth) acrylate (a).

The urethane (meth) acrylate (b) described above
Represents from 5 to 40% by weight, in particular from 10 to 35% by weight, of the composition according to the invention.
If the proportion of the urethane (meth) acrylate (b) is less than 5% by weight, the toughness of the obtained cured product is impaired. When the proportion of the urethane (meth) acrylate (b) exceeds 40% by weight, the viscosity of the composition increases and the handleability deteriorates.

In the present invention, the urethane (meth) acrylates (a) and (b) can be produced separately as described above, but the production methods 5 to 5 exemplified below are used.
8, the urethane (meth) acrylates (a) and (b) can be produced simultaneously.

[Production Method 5] A diol having a polyoxyalkylene structure and a diol having a tricyclodecane structure are sequentially or mixed and reacted with a diisocyanate to react a (meth) acrylate having a hydroxyl group with an isocyanate group of an intermediate obtained. Method.

[Production Method 6] A method in which a diol having a polyoxyalkylene structure and a diol having a tricyclodecane structure are sequentially or mixed with an isocyanate group of an adduct obtained by reacting a diisocyanate with a (meth) acrylate having a hydroxyl group to cause a reaction. .

[Production Method 7] A method of simultaneously reacting a diisocyanate, a diol having a polyoxyalkylene structure, a diol having a tricyclodecane structure, and a (meth) acrylate having a hydroxyl group.

[Production Method 8] A method in which a compound having a (meth) acryloyl group and an isocyanate group in one molecule, a diol having a polyoxyalkylene structure, and a diol having a tricyclodecane structure are sequentially or mixed and reacted.

The above production methods 5 to 8 can be carried out, for example, in the same manner as in the preferred embodiments of production methods 1 to 3, which are production methods of urethane (meth) acrylate (a).

In the composition of the present invention, a prepolymer other than the urethane (meth) acrylates (a) and (b) can be used in combination as long as the effects of the present invention are not impaired.

Here, as the prepolymer other than the urethane (meth) acrylates (a) and (b), a compound selected from polycaprolactone diol, polycarbonate diol, polyester diol, and diamine is used as the diisocyanate and the (meth) acrylate having a hydroxyl group. Prepolymers obtained by the reaction can be exemplified.

Examples of the prepolymer other than the urethane (meth) acrylates (a) and (b) include a polymer compound formed by a urethanization reaction between a polyisocyanate and a (meth) acrylate having a hydroxyl group. Specific examples of such a polymer compound include a urethanization reaction product of tolylune diisocyanate and 2-hydroxyethyl (meth) acrylate (molar ratio 1: 2), diphenylmethane diisocyanate and 2-hydroxyethyl (meth) A urethanization reaction product of acrylate (molar ratio 1: 2) and a urethanization reaction product of isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate (molar ratio 1: 2) can be exemplified.

As the reactive diluent, which is the component (c) in the present invention, both monofunctional compounds and polyfunctional compounds are used. When a cured product having a relatively low elastic modulus is desired, a monofunctional compound is mainly used, but the elastic modulus of the cured product can be adjusted by using a polyfunctional compound in an appropriate ratio. These monofunctional compounds and polyfunctional compounds are not particularly limited, and the following can be exemplified.

Monofunctional compound: N-vinylpyrrolidone, N-vinyl-
ε-caprolactam, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate,
Butoxyethyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methyltrimethyl Ethylene glycol (meth) acrylate, isobornyl (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N,
N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acryloylmorpholine, dicyclopentenyl (meth) acrylate, tricyclodecanyl ( (Meth) acrylates and compounds represented by the following formula:

[Wherein, R ¹ has the same meaning as described above, and R ⁵ has 2 carbon atoms.
To 6, preferably 2 to 4 alkylene groups, R ⁶ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and m is 0 to 12. ] Wherein R ¹ is as described above, and R ⁷ has 2 to 2 carbon atoms.
8 is an alkylene group, and p is 1-8. ] [In the formula, R ¹ , R ⁷ and p are as described above, and R ⁸ is a hydrogen atom or a methyl group.] Aronix M111 (manufactured by Toa Gosei Chemical) M113 (same as above), M114
(Same), M117 (same), KAYARAD TC110S (manufactured by Nippon Kayaku),
R629 (same as above), R644 (same as above), Biscoat 3700 (manufactured by Osaka Organic Chemicals) Polyfunctional compounds: trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth)
Acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tricyclodecane dimethanol di (Meth) acrylate, dicyclopentadiene di (meth) acrylate, dicyclopentanedi (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) ) Epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of acrylate and bisphenose A A 604 (manufactured by Nippon Kayaku ), DPCA-20 (same), DPCA-30 (same), DPCA-
60 (same), DPCA-120 (same), HX-620 (same), D-310
(Same as above), D-330 (same as above), Aronix M-210 (manufactured by Toagosei Chemical), M-215 (same as above), M-315 (same as above), M-325
(Same as above) The component (c) used in the present invention preferably contains N-vinyllactams such as N-vinylpyrrolidone and N-vinyl-ε-caprolactam. When this N-vinyl lactam is used, it is preferably used in an amount of 3 to 20% by weight, particularly 5 to 15% by weight of the composition.

Further, the use of an ethylenically unsaturated monomer having an alicyclic structure as the component (c) further improves the water resistance, hot water resistance, acid resistance, alkali resistance, and the like of the cured product, thereby improving long-term reliability. It is preferable because it improves. Examples of such an ethylenically unsaturated monomer having an alicyclic structure include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, cyclohexyl (meth) acrylate, and tricyclodecane dimethanol. Examples thereof include di (meth) acrylate, and among them, isobornyl acrylate and tricyclodecane dimethanol diacrylate are particularly preferable.

The component (c) is present in the composition of the present invention in an amount of 20 to 70% by weight,
In particular, it is preferable to mix in the range of 25 to 60% by weight.

The polymerization initiator of the component (d) used in the present invention is not particularly limited, and examples thereof include 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, and xanthone. Fluorenone, benzoaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone , Benzoin propyl ether, benzoin ethyl ether, benzyl methyl ketal, 1- (4-isopropylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthones, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc., and particularly preferably 1
-Hydroxycyclohexylphenyl ketone, benzylmethylketanol, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide And the like.

These photopolymerization initiators are used singly or in combination of two or more. If necessary, a sensitizer (photopolymerization accelerator) such as an amine compound may be used in a range not to impair the effects of the present invention. Can be. Further, a thermal polymerization initiator other than the photopolymerization initiator can be used.

The amount of the component (d) is usually 0.1 to 10% by weight,
Preferably it is 1 to 5% by weight.

In addition, the composition of the present invention may contain, as additives, epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, styrene / butadiene / styrene in addition to the components (a) to (d). Block copolymers, styrene / ethylene / butylene / styrene block copolymers, styrene / isoprene / styrene block copolymers, petroleum resins, xylene resins, ketone resins, fluorine oligomers, silicone oligomers, polysulfide oligomers, etc. Can be blended. In addition, antioxidants, coloring agents, ultraviolet absorbers, silane coupling agents, thermal polymerization inhibitors, leveling agents, storage stabilizers, plasticizers, lubricants, solvents, fillers, antioxidants, wetting improvers, and coating surface improvements Agents and the like can also be blended.

The viscosity of the composition of the present invention thus prepared is as follows:
Usually, 1000 to 20000 cp / 25 ° C, preferably 2000 to 10000 cp /
25 ° C and the Young's modulus after curing is usually 10 to 90 kg / mm ²
It is.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples.
The present invention is not limited to these examples.

Production Example 1 In a reaction vessel, 720 g of tricyclodecane dimethanol diacrylate (manufactured by Mitsubishi Yuka, Iupima UV SA1002), 1144 g of isophorone diisocyanate, and dibutyltin dilaurate 4
g, phenothiazine 0.4 g, and 2,6-di-t-butyl-4
1 g of methylphenol was charged. While cooling the reaction vessel with ice water, 863 g of hydroxyethyl acrylate was added thereto.
Was added while keeping the internal temperature below 20 ° C. while stirring the internal solution. After completion of the addition, the internal temperature was maintained at 5 to 20 ° C., and stirring was continued for 1 hour.
0 g of the internal solution was added while stirring so that the internal temperature did not exceed 50 ° C. After completion of the addition, the internal temperature was kept at 40 to 50 ° C., and stirring was continued for 1 hour. 0.1% by weight of residual isocyanate
Stirring was continued until it became below. The obtained urethane acrylate (a) solution is designated as PU-1. The weight ratio of urethane acrylate and tricyclodecane dimethanol diacrylate of PU-1 is (100: 18).

Production Example 2 A reaction vessel was charged with 720 g of tricyclodecane dimethanol diacrylate, 1255 g of isophorone diisocyanate, 4 g of dibutyltin dilaurate, 0.4 g of phenothiazine and 1 g of 2,6-di-t-butyl-4-methylphenol. While cooling the reaction vessel with ice water, 921 g of hydroxyethyl acrylate was added thereto while stirring so that the internal temperature did not exceed 20 ° C. After the addition is completed, the internal temperature is 5-20 ° C
, And stirring was continued for 1 hour, and then 160 g of tricyclodecane dimethanol was added while stirring the internal solution so that the internal temperature did not exceed 50 ° C. After the addition is completed, raise the internal temperature to 40-50.
C. and kept stirring for 1 hour.
00 polytetramethylene glycol (PTMG2 manufactured by Mitsubishi Kasei)
000) was maintained at an internal temperature of 40 to 50 ° C., and stirring was continued until the residual isocyanate became 0.1% by weight or less.

The obtained urethane acrylate (a) solution was subjected to PU-2
And The weight ratio of urethane acrylate and tricyclodecane dimethanol diacrylate of PU-2 is (100: 17.
7).

Production Example 3 A reaction vessel was charged with 1377 g of tricyclodecane dimethanol diacrylate, 2310 g of isophorone diisocyanate, 7 g of dibutyltin dilaurate, 0.7 g of phenothiazine and 2 g of 2,6-di-t-butyl-4-methylphenol. While cooling the reaction vessel with ice water, 1658 g of hydroxyethyl acrylate was added thereto while stirring so that the internal temperature did not exceed 20 ° C. After completion of the addition, the internal temperature was maintained at 5 to 20 ° C., and stirring was continued for 1 hour. Then, 386 g of tricyclodecane dimethanol was added while stirring the internal solution such that the internal temperature did not exceed 50 ° C. . After completion of the addition, the internal temperature was kept at 40 to 50 ° C., and stirring was continued for 1 hour. Of diol (PPTG2000, Hodogaya Chemical Co., Ltd.) was added in order and the internal temperature was raised to 40-50 ° C.
And stirring was continued until the residual isocyanate became 0.1% by weight or less.

The solution of the obtained urethane acrylate (a) was subjected to PU-3
And The weight ratio of urethane acrylate and tricyclodecane dimethanol diacrylate of PU-3 is (100: 20)
It is.

Examples 1-3 Each component was mixed with the composition shown in Table 1, and stirred at 40-50 ° C for 3 hours to obtain a composition.

* 1: IRGACURE184 (manufactured by Ciba-Geigy) 1-hydroxycyclohexylphenyl ketone * 2: IRGACURE907 (manufactured by Ciba-Geigy) 2-methyl-1- [4- (methylthiophenyl)] 2-
Morpholinopropan-1-one * 3: LUCIRIN LR8728 (manufactured by BASF) 2,4,6-trimethylbenzoyldiphenylphosphine oxide * 4: IRGANOX1035 (manufactured by Ciba Geigy) 2,2-thio-diethylenebis [3- ( 3,5-Di-t-butyl-4-hydroxyphenyl) propionate] * 5: TINUVIN770 (manufactured by Ciba Geigy) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate * 6: IRGANOX1076 ( Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate Test Examples The compositions prepared in each Example were drawn on optical fibers using a fiber drawing device. The coated optical fiber was obtained by applying the composition at different speeds and irradiating it with ultraviolet rays.

The average optical fiber diameter of the core material of this coated fiber is about
The outer diameter of the 125 μm coated optical fiber was 210 μm.

<Measurement of Gel Fraction> cutting the coated optical Fuaiba the length of 4 cm, the initial weight was weighed weight and W _0. Soxhletley extraction equipment,
Extraction was performed for 12 hours using methyl ethyl ketone as an extracting agent.

Then, the coated optical fiber was dried at 50 ° C in a vacuum dryer.
After drying for 12 hours, allowed to stand at room temperature for 1 hour, (the dry weight and W ₁₎ was weighed weight.

Further the coating Fuaiba was baked for 30 minutes in an electric furnace at 700 ° C., the coating layer is removed, only the fiber optic were collected and weighed weight (the fiber optic weight and W _F).

The gel fraction of the coating layer of the coated optical fiber was calculated from the following equation.

<Measurement of Tensile Properties> Using an optical fiber stripper (FITEL S-21, manufactured by Furukawa Electric Co., Ltd.), only the optical fiber (core material) was extracted from the coated optical fiber to obtain a hollow coating having a length of 1 cm. . A metal fitting was bonded to each end of the hollow coating with an adhesive so that the hollow coating was perpendicular to the flat surface of the metal fitting. Next, the metal fitting adhered to the hollow coating was sandwiched between the chucks of a tensile tester, and a tensile test was performed. In the tensile test, the Young's modulus was based on a value obtained by testing at a tensile speed of 1 cm / min, a breaking elongation and a breaking stress at a tensile speed of 50 cm / min. Table 2 shows the results.

[Effect of the Invention] The composition of the present invention is excellent as a hard material and a bundling material of an optical fiber because the composition has a low viscosity, a high curing rate and a tough cured product.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masanobu Takahashi 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. Synthetic Rubber Co., Ltd. (72) Inventor Timothy Bishyopp United States 60102 Algonquin, D.I. Riverwood 1720 (56) Reference JP-A-63-233907 (JP, A) JP-A-63-173001 (JP, A) JP-A-63-275619 (JP, A)

Claims (1)

(57) [Claims] (1) Urethane (meth) acrylate having a polyoxyalkylene structure 14 to 70% by weight (b) Urethane (meth) having a tricyclodecane structure
A liquid curable resin composition comprising 5 to 40% by weight of an acrylate, (c) a reactive diluent, and (d) a polymerization initiator.