CN1265744A - Optical glass fiber assemblies, matrix forming compositions and ink coating compositions for use in forming ribbon assemblies - Google Patents

Abstract

Provided is a ribbon assembly having the functional capability of providing mid-span access without the use of additives, monomers or oligomers containing fluorine or silicone. The ribbon assembly is formulated from an oligomer which reduces the surface energy of the ink coating and/or the matrix material. Also provided are ink coating compositions and matrix forming compositions which are suitable for forming the ribbon assembly.

Description

Optical glass fibre band assembly is for the composition and the ink coating composition of the formation matrix that forms the use of fabric strip assembly

Background of invention

1. invention field

The present invention relates to optical glass fibre band assembly, for the composition and the ink coating composition of the formation matrix that forms the use of fabric strip assembly.

2. correlation technique narration

The radiation-curable couting of two stacks of the general coating of optical glass fibre, they form undercoat together.Coating direct and glass contact is called interior undercoat.And surface coating (one or more layers) is called outer undercoat.

The coating that interior undercoat is normally softer provides the environmental protection at glass fibre, particularly, provides anti-well-known little curved (mirobending) phenomenon.The little curved decay that can cause the signal transmission capabilities of coated fiber in coated fiber is not so wish to take place.Outer undercoat on the coated fiber exposed surface generally is harder coating, is used to provide needed anti-Physical Processing power, for example the power that is run into when fiber becomes thigh.

For the hyperchannel transmission, used the optical glass fibre assembly that contains many coated optical fibers.The example of optical glass fibre assembly comprises fabric strip assembly and cable.Typical fabric strip assembly is to make by with matrix material the optical glass fibre of many parallel-oriented single coatings being bonded together.Matrix material has the effect that single optical glass fibre is fixed together as the crow flies, protects their effect during use in addition, and protects them to avoid the effect of installation environment influence.These fibers usually are arranged in banded structure, and it is to contain the structure that is generally the straight thread shape of being generally of about 2～24 fibers.Depend on application, the fabric strip assembly of many gained can be combined into cable, the single coated optical glass fiber that cable had is several to about 1,000.The example of fabric strip assembly is described in the european patent application No 194891 that has delivered.In general, many fabric strip assemblys can be combined then becomes cable, as disclosed in the US Patent No 4906067.

The coated optical glass fiber that uses for the optical glass fibre assembly is coated with usually with colored outer, is called ink coating, perhaps, changes a method, and colorant is added in the outer undercoat, is beneficial to distinguishing of each root coated optical glass fiber.Like this, the matrix material that coated optical glass fiber is bonded together contacts outer ink lay, if latter's existence, the perhaps outer undercoat of contacting and coloring.

The thickness of ink coating is generally about 3～about 10 μ m, and it is to be formed by the pigment in the carrier system that is dispersed in UV curable.The UV curable carrier system contains UV curable oligomer or monomer, is liquid before solidifying, and is beneficial to like this ink composite is applied on the optical glass fibre, and it becomes solid-state afterwards in being exposed to UV radiation.In this way, can be with the UV curable ink composite, by with apply in the undercoat method identical with outer undercoat, be applied on the coated optical glass fiber.

What in use usually need is, the corresponding endpoint centre position at the fabric strip assembly of given length must make fiber bond separately.Make each root fiber approaching by this way, so-called " central span is approaching " (mid-span access) is even exist some particular problems.Make the tail end or the approaching universal method and the equipment of end points of fabric strip assembly, concerning provide central span near, generally be not exclusively to be fit to, or impracticable.

Many trials have been carried out, in order that this a kind of fabric strip unit is provided, therein can be on any position on the fabric strip unit, easily matrix material and the colored film that exists on optical glass fibre are separated, and colored film can not be removed from coated optical glass fiber.Yet,, the purpose of distinguishing each root fiber can not be reached if the separation of matrix material also makes colored film remove from fiber.

It is that matrix material is contacted with solvent such as ethanol or isopropyl alcohol that an approaching commonsense method of central span is provided.These solvents must have the ability of swelling or softening matrix material.Simultaneously, also should selective solvent, make its not coating on each optical glass fibre of swelling.The swelling of matrix material reduces matrix material intensity, and the result can mechanically remove matrix material by slight friction or similar mechanical means, whereby, and for each root still has coating and optical glass fibre that can distinguish between colors provides approaching chance.The example of this solvent process for stripping is described in AT ﹠amp; T pamphlet " D-182355 AccuribbonTM Single FibreAccess " (on March 3rd, 1991).

The European application No 0614099A2 that has delivered discloses a kind of optical fiber tape cell, and wherein bonding between the dyed layer of each optical glass fibre and the matrix material is inhibited by add the release agent that is equal to or less than 5wt% in each layer.The purpose that adds release agent is when matrix material separates with optical glass fibre, to prevent that dyed layer from peeling off.The example of these release agents comprises silicone release agent or based on the release layer (release layer) of fluorine.

The Japanese patent application No 64-22976 that has delivered discloses the radiation curable ink composition, and it comprises special radiation-hardenable oligomer.Ink composite provides external undercoat to have fusible ink coating, and it can be separated with the matrix material in the fabric strip assembly.

The Japanese patent application No H1-152405 that has delivered discloses the radiation curable ink composition, and it comprises organic silicone composites.This silicone composites provides the ink coating with ability that the matrix material in easier and the fabric strip assembly is separated.

United States Patent (USP) 4,900,126 (Jackson) disclose a kind of optical glass fibre tape cell, and wherein the optical glass fibre of every single coating all has painted skin.Every optical glass fibre is also used release agent coating, and release agent has low affinity to jointing material or colorant materials.The example of release agent is teflon.Release agent produces weak interface layer on the interface of colorant materials and matrix material, matrix material and optical glass fibre can be separated whereby, and not peel off dyed layer on each root optical glass fibre.

US Patent No 4,953,945 disclose used strippable solidified coating between the accretion chromatograph of optical glass fibre and matrix materials, matrix material can be stripped down from optical glass fibre whereby, and not peel off the dyed layer of optical glass fibre.

US Patent No 5,524,164 disclose the sets of cables zoarium that comprises many fabric strip assemblys.The common coating material that the fabric strip assembly is bonded together contains the composition with common coating major component compatibility difference.The example of the composition of this compatibility difference comprises hydrocarbon, silicone oil and the fluorocarbon oil that contains 10～20 carbon atoms.The composition of compatibility difference descends the friction force between the fabric strip assembly, thereby prevents that fiber is damaged when cable is crooked.The composition of compatibility difference provides discontinuous layer on common coating, it is the form on " sea " and " island ".This patent is not about the central span that is included in each the root coated optical glass fiber in the fabric strip assembly approaching disclosure or narration.

US Patent No 5,561,730 disclose the cable that comprises many fabric strips unit.The common coating material that the fabric strip assembly is bonded together comprises release agent.The example of this class release agent is silicone oil and fluorocarbon oil.The release agent composition descends the friction force between the fabric strip assembly, in case fiber is damaged when cable is crooked.This patent is not about providing approaching disclosure of central span or narration for each the root coated optical glass fiber that is included in the fabric strip assembly.

US Patent No 5,621,838 disclose the coated optical glass fiber unit that many coated optical glass fibers of being bonded together by common bonding coat constitute.The ink coating of optical glass fibre and common bonding coat have suppressed ply adhesion through handling, and bonding coat can be removed from ink lay as a result, and silicone release agent or fluorine release agent are added in ink coating and the common bonding coat.

Based on the release agent of silicone and fluorine through can cause behind the certain hour do not wish the interior undercoat that takes place and outside the degraded of undercoat.When they also are not adhered in the coating, can ooze out from coating.They and desired coating composition often are the time non-compatibilities.So traditional silicone and fluorine release agent can only be used on a small quantity, for example below the 5wt%.If, use the traditional release agent more than 5%, they can make matrix material and ink coating swelling, and can accumulate between matrix and the ink coating, cause matrix from peeling off that optical glass fibre is difficult to avoid, the result weakens the protective action of matrix material.

It also is worthless using the release agent based on acrylate silicone and fluorine in the optical glass fibre coating.For example, this class release agent usually with ink coating in component incompatible.Use this class release agent can also cause the undesirable variation of ink coating performance.

Along with the increase to the demand of coated optical glass fiber, the reaction that manufacturer must have is, increases the tensile fiber production line more, and the trial that increases the linear velocity of existing tensile fiber production line.Under latter event, a factor of the decision linear velocity upper limit for given radiation source and radiation intensity, is the solidification rate characteristic of radiation curable ink composition.

If linear velocity is increased to the degree that the time requirement of the solidification rate of radiation curable ink composition can not be provided, the radiation curable ink composition can not be subjected to being enough to making the radiation of radiation curable ink composition full solidification or crosslinked sufficient dosage so.Line speed is inversely proportional to the radiation dose that shines optical glass fibre in general.That is, along with the increase of line speed, for given radiation source, the radiation dose that shines the radiation curable ink composition in process of production must reduce.The incomplete curing of radiation curable ink composition is worthless, must avoid, its reason is, the performance of needed at that time incomplete cured printing ink coating may not reach and/or incomplete cured printing ink coating may keep viscosity, maybe may there be foul smell in (can have problems in the processing subsequently), extractable matter (undesirable) also can increase in according to the ink coating that infer to solidify, and also lacks bonding to coated optical glass fiber.

Though ink composite must have very fast curing rate, go up full solidification so that guarantee ink coating at high speed draft apparatus (drawing tower), increasing curing rate should be not cost with other important performance of sacrificing ink coating, provides suitable central span approaching in the time of for example in being applied to the fabric strip assembly.So, needing a kind of like this radiation curable ink composition, it presents suitable viscosity, makes the outer undercoat that provided and the viscosity between the ink coating greater than the viscosity between ink coating and the matrix material, so that provide central span approaching.

In addition, ink composite should not contain on the surface that can move to optical glass fibre and produce the composition of corrosion.Ink composite also should not contain can make the unsettled composition of protective coating.The ink coating of optical glass fibre should be that dyeing is firm in decades, should not cause transmission signals decay, is porous and twist with the fingers glue (cabling gel) and chemicals not, in addition, for the fibre core that is arranged in rows, allows enough light to penetrate.

From the above, apparent, optical glass fibre technology exists the many unique requirement to the radiation curable ink composition, and more traditional technology as printing-ink, does not reach these requirements.Needing to provide central span approaching, and avoids the radiation curable ink composition of the problem relevant with the silicone base release agent with traditional fluorine.

Usually, ink composite must solidify in inert atmosphere, promptly under the condition that does not have oxygen.The cost costliness that provides inertia neon to enclose to the optical glass fibre stretcher.Therefore, compare with the ink composite that must be cured in inert atmosphere, the radiation curable ink composition that presents high curing rate in the presence of air must have significant advantage.

Summary of the invention

The objective of the invention is to, provide to have and give central span near function, do not use the optical glass fibre band assembly of adjuvant, monomer or the oligomer of fluorine-containing or silicone.

Another object of the present invention provides the composition that the radiation-hardenable that is applicable to shaped fibers band assembly forms matrix.

Another object of the present invention provides, and when solidifying in the fabric strip assembly aptly and using, provides central span approaching radiation curable ink composition to each root coated optical glass fiber.

Another object of the present invention provide can in the presence of air, solidify and also provide central span approaching radiation curable ink composition.

Have now found that, contain radiation curable ink composition by preparation according to viscosity adjustment oligomer of the present invention, amazingly be, can on coated optical glass fiber, form ink coating, the fabric strip assembly that provides like this has the approaching function of central span, and does not need to use the release agent adjuvant of fluorine-containing or silicone.Especially, be suitable for, and be, provide central span approaching with its capability by the polymeric matrix that forms according to novel ink coating composition of the present invention.

The invention provides the novel radiation curable ink coating composition that is suitable on optical glass fibre, forming ink coating, it is to be prepared by the composition that contains the viscosity adjustment oligomer, this oligomer contains at least one and is combined in radiation-hardenable functional group on the low-surface-energy main chain, and is substantially free of silicone and fluorine.

The present invention also provides the fabric strip that comprises following material assembly:

Many coated optical glass fibers; With

Matrix material, it combines described many coated optical glass fibers, and wherein at least a described coated optical glass fiber comprises the coating optical glass that contains following material:

Optical glass fibre;

At least the coating of one deck on described optical glass fibre;

Ink coating on the described coating of one deck at least, it is prepared by the composition that comprises following material:

The viscosity adjustment oligomer, it contains at least one and is combined in radiation-hardenable functional group on the low-surface-energy main chain, and it is substantially free of silicone and fluorine.

The composition that the present invention also provides a kind of radiation-hardenable to form matrix, it is prepared by the composition that comprises following material:

The viscosity adjustment oligomer, it contains at least one and is combined in radiation-hardenable functional group on the low-surface-energy main chain, and it is substantially free of silicone and fluorine.

The present invention also provides a kind of new fabric strip assembly, and it has provides central span approaching performance to each root optical glass fibre, and does not need to use silicone and fluorine release agent in ink coating or matrix material, and described fabric strip assembly comprises:

Many coated optical glass fibers;

Matrix material, it combines described many optical glass fibres; It is to be formed by the composition that comprises the viscosity adjustment oligomer; This oligomer contains at least one functional group who is combined in the radiation-hardenable on the low-surface-energy main chain, and is substantially free of silicone and fluorine.

The reference implementation scheme describes in detail

According to improved radiation curable ink coating composition of the present invention can provide central span near and need not use adjuvant.Especially, ink composite is applicable to provides the coating of the cured printing ink with three-dimensional cross-linked polymer matrix, and proper property that provides central span approaching is provided for it.Providing central span approaching with this form, is diverse with using adjuvant on policy.Yet, if desired, can add traditional release agent, so that the performance of ink composite is met the requirements.

Improved ink composite of the present invention can be to be used to be coated with and distinguish any known ink composite of coated optical glass fiber.In general, the radiation curable ink composition contains at least a pigment that is dispersed in the radiation curing carrier system.Yet, can form desired, as not contain pigment transparent ink coating.By in the radiation curing carrier system, using the viscosity adjustment oligomer of new radiation-hardenable, the traditional oils ink composition is become according to improved ink composite of the present invention.Amazing is in the radiation curing carrier system, even can use the viscosity adjustment oligomer to make main oligomer.Perhaps change method, can mix with pigment, diluent monomer and other oligomer (selecting for use as required) and prepare by viscosity being regulated oligomer according to improved ink composite of the present invention.

In order to provide central span near fluorine and silicone are mixed in ink coating composition.Have now found that fluorine and silicone reduce the surface energy of gained ink coating.Think that this lower surface energy reduces the bond strength between ink coating and the matrix material in the following manner.When applying liquid matrix material, low-surface-energy generally produces less wetting.Wettingly lessly cause surface contact relatively poor, so the viscosity between matrix material and the ink coating is lower.

The present invention provides the surface energy that reduces under the condition of not using fluorine and silicone.Surface energy reduces by utilizing the main chain in having the viscosity adjustment oligomer of low-surface-energy.The low-surface-energy main chain comprises the hydrocarbon side chain of suspension, and the side chain that is hung can reduce surface energy.The example of preferred low-surface-energy main chain comprises hydrocarbon main chain and polyester backbone.More preferably, the low-surface-energy main chain of viscosity adjustment oligomer is a polyester.

The preferred amount of viscosity adjustment oligomer is, provide and have the ink coating of apical grafting feeler greater than 65 ° surface energy, more preferably the top contact feeler is equal to and greater than about 70 °, even more preferably be equal to and greater than about 75 °, most preferably be equal to and greater than about 80 °, under the condition of not using traditional silicone and fluorochemicals.

Can use viscosity adjustment oligomer preparation not contain silicone and fluorine release agent substantially, also not contain the ink coating composition of other traditional release agent, when suitably solidifying, it can provide central span approaching.More surprisingly, even ink composite is solidified, also can provide these performances.

The exemplary of viscosity adjustment oligomer comprises and contains the oligomer that at least one is attached to the radiation-hardenable functional group on the low-surface-energy main chain.The radiation-hardenable functional group can be that for example, it can carry out polymerization through free radical polymerization or cationic polymerization alkene class unsaturated group.The object lesson of suitable alkene class unsaturated group is the group that contains acrylate, methacrylate, styrene, vinethene, vinyl esters, N-substituted acrylamide, N-vinylamide, maleate and fumarate.Preferably, alkene class unsaturated group is provided by the group that contains acrylate, methacrylate, N-vinyl-functional.

At first narrate viscosity adjustment oligomer based on polyester.The radiation-hardenable functional group can directly be attached on the polyester backbone, perhaps can be connected on the polyester by connecting base.The example of suitable connection base comprises carbamate, urea and ester group.

Number-average molecular weight based on the viscosity adjustment oligomer of polyester is generally about 500～about 10,000, more preferably about 1,000～about 8,000.Usually the ester group equivalent that has of polyester be about 2～about 40, be preferably about 3～about 20, more preferably about 5～about 15.

Polyester contains the hydrocarbon side chain that is suspended on the polyester backbone.Be not bound by any theory, think, the hydrocarbon side chain of suspension provides the cured printing ink coating that has from the substrate material surface separating power, thereby the adhesive linkage of matrix material is provided.Particularly, think that the hydrocarbon side chain reduces the surface energy of ink coating, entanglement and nonbonding combination between ink coating and matrix material is provided simultaneously, thereby has caused having enough viscosity between them, avoided not wishing the delamination that takes place.Though entanglement and nonbonding are in conjunction with providing viscosity, the combination of this entanglement and nonbonding can be broken during central span is approaching, thereby the exposed ink coating optical glass fibre of cleaning and the adhesive linkage of matrix material are provided.

Preferably, the hydrocarbon side chain is positioned at the enough near position of ester group, and they can be subjected to chemical attack with sterically hindered prevention ester functional group like this.For example the hydrocarbon side chain can be positioned on ester functional group's the alpha-carbon atom, thus the spatial obstacle of providing.Therefore, have been found that the hydrocarbon side group can be used for two purposes (1) astoundingly and reduce the surface energy of ink coating and the hydrolytic stability that (2) provide polyester backbone in the coating.

The hydrocarbon side chain should exist with the amount that the viscosity adjustment oligomer with the ability that reduces the ink coating surface energy is provided.At least 5% of preferred viscosity adjustment oligomer number-average molecular weight is made of the hydrocarbon side chain, more preferably at least about 10%, most preferably is at least about 15%.The hydrocarbon side chain that uses for the reduction surface energy generally is applied on the various main polymer chains, is not limited to polyester.The amount of hydrocarbon side chain should be not excessive, in order to avoid produce undesirable performance, for example, uncured ink coating composition viscosity is too high, and perhaps the modulus of cured printing ink coating and/or pulling strengrth are too low.Like this, the part that viscosity adjustment oligomer number-average molecular weight is contributed by the hydrocarbon side chain should be less than about 40%, be more preferably less than about 30%, most preferably less than about 20%.

Preferably, the interval of hydrocarbon side chain on polyester backbone is even substantially.Particularly preferred structure is a pectination, and the hydrocarbon side chain resembles from the outstanding tooth of the trunk of comb therein.Yet the hydrocarbon side chain is different with the broach of two-dimensional space, and it can be outstanding with different directions from polyester backbone.

The preferred hydrocarbons side chain is to contain the low alkyl group of about 3～about 30 carbon atoms or the aryl that alkyl replaces, and is preferably about 5～about 20 carbon atoms, most preferably is about 5～about 15 carbon atoms.On demand, the aryl of alkyl and/or alkyl replacement can be linearity, side chain or ring-type.So propyl group, just-butyl, different-butyl, 2-ethyl-butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, myristyl, propylphenol, butylphenol, amyl phenol, hexylphenol, heptylphenol, octyl phenol, nonyl phenol etc. all suit.Preferred linearity or branched alkyl.When using the aryl of alkyl replacement, preferred alkyl is attached to the contraposition of the position of polyester backbone at aryl.The preferred hydrocarbons side chain is a low alkyl group.

Preferably, the ester functional group who exists on polyester backbone more preferably at least about 70%, even more preferably at least about 90%, most preferably is all sterically hindered by the hydrocarbon side chain at least about 50% basically.

The polyester backbone of viscosity adjustment oligomer can form with any suitable means.Based on disclosure provided herein, those skilled in the art can provide needed polyester backbone.For example: following method is suitable for preparing the polyester backbone with hydrocarbon side chain.

(1) hydroxycarboxylic acid and polyvalent alcohol react can provide the polyester with hydrocarbon side chain.Polyvalent alcohol can be a side chain, and/or hydroxycarboxylic acid can be side chain, so that provide from the outstanding hydrocarbon side chain of polyester backbone.Perhaps change method, hydroxycarboxylic acid and/or polyvalent alcohol can contain non-end group hydroxyl-functional base, when it forms ester group with carboxylic acid reaction, have obtained side chain during the formation polyester backbone like this.

(2) polycarboxylic acid and polyvalent alcohol react can provide the polyester with hydrocarbon side chain.Polyvalent alcohol can be a side chain, and/or polycarboxylic acid can be side chain, so that provide from the outstanding hydrocarbon side chain of polyester backbone.Perhaps change method, polyvalent alcohol can contain non-end group hydroxyl-functional base, during with carboxylic acid reaction formation ester group, forms side chain at it in polyester backbone like this.

The polyester backbone of preferred viscosity adjustment oligomer reacts formation by suitable hydroxycarboxylic acid and the glycol that suits.The term as used herein hydroxycarboxylic acid comprises the hydroxy aliphatic carboxylic acid.Preferably, hydroxyl functional group carboxylic acid contains about 4～about 30 carbon atoms, more preferably contains about 8～about 24 carbon atoms.The example of suitable hydroxy aliphatic carboxylic acid comprises Hydroxyoctanoic acid, hydroxydecanoic acid, hydroxylauric acid, hydroxyl myristic acid, hydroxy-palmitic acid, hydroxy stearic acid, hydroxy oleate, hydroxylinolic acid and hydroxyl leukotrienes.The object lesson of suitable hydroxycarboxylic acid comprises 12-hydroxy stearic acid, 2-hydroxy-4-methyl-valeric acid, 12-hydroxyl-4-octyl group-dodecoic acid, δ-Shi Erneizhi, 19-hydroxyl-10-hexyl-nonadecanoic acid and 16-hydroxyl-4-nonyl-11-butyl-ten hexacarboxylic acid.The commercial examples of suitable hydroxycarboxylic acid comprises the P-10 acid of CasChem company.

The structure that preferred hydroxycarboxylic acid has is when the hydroxyl functional group reacts the formation ester group, can produce the structure of the polyester with hydrocarbon side chain.If use side chain hydroxyl functional group carboxylic acid, the hydroxyl functional group can be an end group, yet, if use linear hydroxycarboxylic acid, should there be the hydroxyl end functional groups so, so that when the hydroxyl functional group reacts the formation ester bond, form the hydrocarbon side chain that is connected in polyester backbone.

The hydroxy aliphatic carboxylic acid can contain an above hydroxyl.Preferably, the hydroxy aliphatic carboxylic acid contains only unsaturated link.

Preferred hydroxycarboxylic acid contains at least one hydrocarbon side chain, and its representational structural formula is as follows:

In the formula: the H=hydrogen atom;

The O=oxygen atom;

R ₁, R ₂, R ₃, R ₄, R ₅And R ₆=H or hydrocarbon hand hay cutter chain, but must R ₁To R ₆At least one

Individual is the hydrocarbon side chain, preferred R ₁And R ₂Not all be H; With

X+Y+Z 〉=3, preferred 〉=5, more preferably 〉=10.

Preferred hydrocarbons side chain and the ester group that is formed by the reaction between hydroxyl and the carboxylic acid group are enough near, so that the hydrocarbon side chain can sterically hindered ester functional group be subjected to chemical attack.For example, ester group in the presence of moisture to the hydrolysis sensitivity.Yet, have been found that so, they can make hydrolysis reaction be subjected to steric restriction if the hydrocarbon side chain is in crucial position.Like this, based on the ink coating of polyester with sterically hindered ester group from being more chemically-resistant attack by nature.

The example of suitable viscosity adjustment oligomer can represent that it is that the ingredients listed reaction generates with following nonrestrictive general formula:

P-(BHCA) _m-I-R????????????????????????????????????(2)

P-((BHCA) _m-A-(BHCA) _m-I) _n-R?????????????????????(3)

R-I-((BHCA) _m-A-(BHCA) _m-I) _nIn-R (4) formula, BHCA is hydroxycarboxylic acid branching and/or that contain non-end group hydroxyl functional group, and it provides because of what hydroxyl functional group's reaction formed that ester group obtains and is connected to hydrocarbon side chain on the polyester backbone;

I is a polyisocyanate compound;

A is a polyvalent alcohol;

P is the compound that contains at least one hydroxyl functional group;

R is the hydroxyl functional group compound that contains the radiation-hardenable functional group;

N is 1～about 20, preferred about 1～about 10, by on average; With

M is 1～about 50, preferred about 1～about 30, and by on average.

Be not limited to general formula 2 to 4 signifiers according to viscosity adjustment oligomer of the present invention.For example: the viscosity adjustment oligomer can comprise the branched polyester main chain that use has two above hydroxyl functional groups' polyvalent alcohol to obtain.Yet, preferably have the linear polyester main chain of carbon containing side chain, shown in 2 to 4.Term " branched polyester " does not comprise term " linear polyester with carbon containing side chain ".Those polyester that only contain the side-chain branching that is made of complete monomeric unit are " branched polyesters ".The application of term " branching " and " side chain ", describe in detail as following document: Odian work " Principles of Polymerization " (" Principles of Polymerization "), the third edition, is hereby incorporated by by the 17th～19 page.

In formula 2 to 4, isocyanate group and hydroxyl reaction form carbamate linkage, and this is well-known reaction.Hydroxycarboxylic acid carries out the polymer polyester main chain that polymerization forms the viscosity adjustment oligomer.Can use the potpourri of hydroxycarboxylic acid, so that regulate the performance of polyester on demand.Formed water can be removed through any suitable method during ester group forms, for example, and by distillation.

After forming polyester backbone, the terminal hydroxyalkyl cooh of formed polyester can the radiation-hardenable functional group react with polyisocyanates and hydroxyl official, forms carbamate linkage between polyester backbone and radiation-hardenable functional group.Radiation-hardenable base functional group also can in position be bonded on the polyester backbone except the end group of polyester backbone.These reaction types are well-known in the art, so any technician of this area can both easily make needed oligomer based on disclosure provided herein.

The radiation-hardenable functional group can be connected on the polyester backbone through any suitable connection base.For example: can be formed in the polyester backbone that is keeping the carboxylic-acid functional base on the polyester backbone.The carboxylic-acid functional base can with the hydroxyl official can radiation curable compounds hydroxyl reaction, thereby between polyester backbone and radiation curable compounds, provide ester linkage.

In first embodiment, " A " can be the alkyl polyols that contains about 2～about 50 carbon atoms, more preferably contains about 5～about 30 carbon atoms.Polyvalent alcohol can be straight or branched on request.Preferably, polyvalent alcohol contains the hydrocarbon side chain on the carbon atom of the α that is suspended on the hydroxyl functional group or β position.

Suitable hydrocarbon side chain comprises those that this paper is above-mentioned.Though preferred diol also can be used polyvalent alcohol for needed branching level is provided.

The example of preferred glycol comprise following structure (5): In the formula:

H is a hydrogen atom;

O is an oxygen atom;

C ₁It is the carbon atom that is positioned at hydroxyl functional group alpha position;

C ₂It is the carbon atom that is positioned at hydroxyl functional group β position; With

R ₇, R ₈, R ₉And R ₁₀Be respectively H or alkyl, but must R ₇, R ₈, R ₉And R ₁₀Not H entirely, preferred R at least ₇, R ₈, R ₉Or R ₁₀One of be hydrocarbon side chain as herein described.

Alkyl R ₇, R ₈, R ₉And R ₁₀Can be subjected to chemical attack by the polyester that hydroxyl functional group and carboxylic acid reaction form by steric restriction.As previously mentioned, ester group when having moisture to the hydrolysis sensitivity.Yet alkyl can make hydrolysis reaction be subjected to steric restriction.Like this, based on the ink coating of polyester with this structure from saying more chemically-resistant attack by nature.

Particularly preferred glycol is represented with following general formula (6):

In the formula: H is a hydrogen atom;

O is an oxygen atom;

C is a carbon atom; With

R ₁₁And R ₁₂Be respectively H or hydrocarbon side chain, but must R ₁₁And R ₁₂Not all be H.Preferably, R ₁₁And R ₁₂Both are the alkyl that contain about 1～about 12 carbon atoms, most preferably contain about 2～about 6 carbon atoms.More preferably, R ₁₁Or R ₁₂At least one is a hydrocarbon side chain described herein.

The object lesson of suitable polyvalent alcohol comprises:

The 2-methyl isophthalic acid, ammediol;

2,2-dimethyl-1, ammediol;

2-ethyl-1, ammediol;

2,2-diethyl-1, ammediol;

2-propyl group-2-methyl isophthalic acid, ammediol;

2-propyl group-2-ethyl-1, ammediol;

2-butyl-2-ethyl-1, ammediol;

2-cyclohexyl-2-methyl isophthalic acid, ammediol;

2-phenyl-2-methyl isophthalic acid, ammediol;

1, the 2-propylene glycol;

1, the 4-butylene glycol;

1, the 6-hexanediol;

1, the 2-cyclohexanediol;

1, the 3-cyclohexanediol;

1, the 4-cyclohexanediol;

The cyclohexyl dimethanol;

2,2-dimethyl-4,4-dimethyl-1,5-pentanediol;

Ethylene glycol;

Diglycol;

Dipropylene glycol;

1, the 9-nonanediol;

Deng and

Its potpourri.

If desired, can use oligomer polyol.Preferably, oligomer polyol is a glycol.If the use oligomer diol, preferred, it contains at least about 2 hydroxyls by average.Oligomer polyol by average, can contain 2 above hydroxyls.If oligomer polyol contains 2 above hydroxyls, branching viscosity adjustment oligomer just can form so.The example of suitable oligomer diol comprises PTMEG, polyolefin diols, polyester-diol, PCDL and composition thereof.The preferred polyester glycol.

If the use PTMEG, preferred, polyethers is noncrystalline polyethers basically so.Preferably, polyethers comprises the repetitive that is made of following one or more monomeric groups:

PTMEG can be by preparations such as oxirane, epoxypropane, tetrahydrofuran, methyl substituted tetrahydrofuran, epoxy butanes.The example that can be used as the polyethers of PTMEG is the polymerizate of 20wt%3-methyltetrahydrofuran and 80wt% tetrahydrofuran, and the both is through ring-opening polymerization.This copolyether contains oxyalkylene repeat units branching or nonbranched, and it is sold with trade name PTG-L 1000 (Japanese Hodogaya chemical company).Another example of the PTMEG that can use is PTG-L 2000 (a Hodogaya chemical company).

If the use polyolefin diols, preferred polyolefm is linearity or the branched hydrocarbon that contains many terminal hydroxy groups so.Preferably, hydrocarbon is to contain many methylene (CH ₂-) non-aromatic compound, it can contain the unsaturated and/or unsaturated link that hangs in the chain.Fully saturated, for example, the hydrocarbon of hydrogenation is preferred, increases along with the minimizing of degree of unsaturation because solidify the long-time stability of coatings for optical fiber.The example of hydro carbons glycol comprises, for example, and 1 of the hydrogenation wholly or in part of terminal hydroxy group, 2-polybutadiene; 1,4-, 1,2-polybutadiene copolymer, 1,2-polybutadiene-ethene or propylene copolymer, polyisobutene polyol and composition thereof etc.Preferably, the hydro carbons glycol is 1 of basic hydrogenation fully, 2-polybutadiene or 1,2-polybutadiene-ethylene copolymer.

The example of PCDL is the product that is generated routinely with glycol alcoholysis diethyl carbonate.Glycol can be, for example, contains the aklylene glycol of about 2～about 12 carbon atoms, for example 1, and 4-butylene glycol, 1,6-hexanediol, 1,12-dodecanediol etc.Also can utilize the potpourri of these glycol.PCDL can contain ehter bond except that containing carbonate group in main chain.Like this, for example, can use the Copolycarbonate of oxyalkylene monomer and aforesaid aklylene glycol.The oxyalkylene monomer comprises, for example, and oxirane, tetrahydrofuran etc.The solidified coating that these multipolymers generate compares with the PCDL homopolymer, has lower modulus; But also the crystallization of inhibition liquid coating composition.Also can utilize the potpourri of PCDL and Copolycarbonate.

PCDL comprises, for example, Duracarb 122 (PPG Industries) and Permanol KM10-1733 (Permuthane Inc, Ma).Duracarb 122 is by producing with hexanediol alcoholysis diethyl carbonate.

The example of polyester-diol comprises the reaction product of saturated polycarboxylic acid or its acid anhydride and glycol.Saturated polycarboxylic acid and acid anhydride comprise, for example, phthalic acid, m-phthalic acid, terephthalic acid (TPA), inclined to one side phthalic acid, tetrahydrophthalic acid, hexahydro-phthalic acid, tetrachlorophthalic acid, hexane diacid, azelaic acid, decanedioic acid, succinic acid, glutaric acid, malonic acid, heptandioic acid, suberic acid, 2,2-dimethyl succinic acid, 3,3-dimethylated pentanedioic acid, 2,2-dimethylated pentanedioic acid etc., and acid anhydride and composition thereof.Glycol comprises, for example, 1,4-butylene glycol, 1,8-ethohexadiol, diethylene glycol, 1,6-hexanediol, hydroxymethyl-cyclohexane etc., polycaprolactone is included in this class, it is commercially available with trade name Tone Polylol series of products by Union Carbide company, and for example, Tone 0200,0221,0301,0310,2201 and 2221.Tone Polyol 0301 and 0310 is a trifunctional.

Compare with the consumption of hydroxycarboxylic acid, preferred polyol " A " is to exist in a small amount.Preferably, the amount of polyvalent alcohol " A " is about 10wt% or still less, more preferably about 7wt% or still less.General assembly (TW) based on the reactant that is used to form the viscosity adjustment oligomer.

Any organic multiple isocyanate can both be separately or with the form of potpourri as polyisocyanates.The example of suitable diisocyanate comprises: isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), tetramethylene Xylene Diisocyanate (TMXDI), MDI, hexamethylene diisocyanate, the cyclohexylidene diisocyanate, methylene bicyclohexane diisocyanate, 2,2, the 4-trimethyl hexamethylene diisocyanate, the metaphenylene diisocyanate, 4-chloro-1, the 3-phenylene vulcabond, 4,4 '-the biphenylene diisocyanate, 1, the 5-naphthalene diisocyanate, 1, the 4-tetramethylene diisocyanate, 1, the 6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexylidene diisocyanate, and poly-trialkylphosphine oxide and polyester-diol diisocyanate, for example: with the polytetramethylene ether diol of TDI termination and the poly-hexane diacid second diester that stops with TDI.Preferably, polyisocyanates is TDI, IPDI or TMXDI.

Can use any suitable hydroxyl official energy radiation curable compounds.Some compounds that contain (methyl) acrylate-functional base comprise, for example, and hydroxyl functional acrylate such as acrylic acid 2-hydroxyethyl ester, acrylic acid 2-hydroxypropyl acrylate etc.The compound that contains the vinyl ether functional base comprises, for example, and 4-hydroxy butyl vinyl ether and triethylene glycol mono vinyl ether.The compound that contains Malaysia ester functional group comprises that for example, maleic acid and hydroxyl official can maleates.

Provide the hydroxyl functional compound of epoxide functional groups to be, for example, can with the chloropropylene oxide of the hydroxyl reaction of oligomer diol, perhaps can with the compound that contains one or more epoxy radicals and hydroxyl of polyisocyanates reaction, as the oligomer of bisphenol-A bifunctional epoxy resin.

Provide the hydroxyl functional compound of amine-alkene or mercaptan-alkene system to comprise, for example, allyl unsaturated group, or tertiary amine or thiol.Like this, the viscosity adjustment oligomer can have the allyl unsaturated group by isocyanates and the reaction of trimethylolpropane diallyl ether, and perhaps the viscosity adjustment oligomer can have the amine functional group by isocyanates and the reaction of amine-functionalized compound.These compounds comprise, for example, the adduct of trimethylolpropane, isophorone diisocyanate and two (first) ehtylethanolamine, the adduct of ethylene glycol, isophorone diisocyanate and dipropyl monoethanolamine, and the adduct of diethyl ethanolamine, dimethylethanolamine or dipropyl monoethanolamine.

Preferably, polyvalent alcohol, polyisocyanates and hydroxyl official can radiation curable compounds react with following ratio, that is, use 1 equivalent hydroxyl groups, about 1.1 to about 1.3 equivalents be contained in isocyanate group in the polyisocyanates and about 0.2～about 1.5 equivalents be contained in the hydroxyl functional group of hydroxyl official in can radiation curable compounds.Preferably, the hydroxyl functional group equivalents that polyvalent alcohol and hydroxyl official can the radiation curable compounds equivalents of the isocyanate group in polyisocyanates no better than.

In the reaction of these compounds, can use the anti-catalyst for application that forms carbamate.The example of suitable catalyzer comprises: copper naphthenate, cobalt naphthenate, zinc naphthenate, two lauric acid normal-butyl tin, triethylamine, 1,4-diazabicyclo (2,2,2) octane and 2,6,7-trimethyl-1,4-diazabicyclo (2,2,2) octane.The general consumption of catalyzer is about 0.01～about 1 weight portion, in 100 weight portion reaction raw materials.Temperature of reaction is generally 10 ℃～about 90 ℃, is preferably about 30 ℃～about 80 ℃.

Particularly preferred viscosity adjustment oligomer is represented with following formula (7):

R-I-(BHCA) _S-A-(BHCA) _V-I) _W-R?????????????????????(7)

Oligomer (7) is made by following composition is reacted:

R is hydroxyl official energy radiation curable compounds;

I is a polyisocyanate compound;

BHCA is a hydroxycarboxylic acid, and for branching person and/or contain non-terminal hydroxyl functional group person, it can provide because of the hydroxyl functional group reacts and form ester group and be connected in carbon containing side chain on the polyester backbone;

A is a polyvalent alcohol

W is 1 to about 20, preferred 1 to about 10, most preferably 1 to about 5; With

S+V is 4 to about 20, and is preferred about 5 to about 15 and most preferably from about 12, by average.Perhaps change a method, radiation-hardenable functional group " R " can be directly connected on the polyester backbone, and this is by hydroxyl functional group " R " and the carboxylic-acid functional radical reaction formation ester linkage on the polyester backbone are realized.By this way, can avoid using polyisocyanates.

Particularly preferred demoulding oligomer is poly-(hydroxy stearic acid) urethane acrylate, and it is represented with following oligomer (8):

HA-I-Poly(HSA)-I-HA?????????????????????(8)

Oligomer (8) is made by following composition:

HA is a hydroxy-ethyl acrylate;

I is an isophorone diisocyanate; With

Poly (HSA) is for pressing following formula (9) signifier In the formula: B+C=2 is to about 20, is preferably about 5 to about 15, and most preferably from about 12, by average.

The another kind of proper method of preparation demoulding oligomer is to make polycarboxylic acid and polyol reaction.Following formula is the representational example of this class reaction:

R-I-(A-(PAC-A) _t-I-R???????????????????(10)

R-(PAC-A) _t-I-R??????????????????????(11)

R-(PAC-(A-PAC) _tIn-R (12) formula: PAC is the multi-carboxylic acid compounds;

I is a polyisocyanate compound;

R is hydroxyl official energy radiation curable compounds;

A is a polyvalent alcohol; With

T is 1 to about 20, preferred about 1～about 15, and by average.

At least one of polycarboxylic acid or polyvalent alcohol are branching, and so that the polyester backbone with carbon containing side chain to be provided, perhaps polyvalent alcohol contains non-end group hydroxyl functional group, and it provides because of hydroxyl functional group and carboxylic acid reaction and forms the polyester backbone that the ester functional group has the carbon containing side chain.The structure of demoulding oligomer is not limited to formula (10) to (12).

I, R and A can be any this paper above-claimed cpds.

PAC can be any multi-carboxylic acid compounds.Suitable dicarboxylic acid comprises ethane diacid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, maleic acid, fumaric acid, phthalic acid, m-phthalic acid, terephthalic acid (TPA), 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid and 1,3, the 5-benzenetricarboxylic acid.Also can use the carboxylic acid that contains two or more carboxylic acids.

The consumption that contains the viscosity adjustment oligomer of polyester backbone can be far longer than the consumption of traditional release agent that contains silicone and fluorine.Especially, this viscosity adjustment oligomer consumption can be about 1～about 90wt%, is preferably about 5～about 80wt%, and more preferably about 10～about 70wt% is in the general assembly (TW) of radiation curable ink coating composition.

The other example of suitable viscosity adjustment oligomer is the hydrocarbon compound that contains at least one radiation-hardenable functional group and hang the hydrocarbon side chain.The number-average molecular weight of the hydrocarbon main chain that this class viscosity adjustment compound is contained be about 1000～about 10,000, be preferably about 2,000～about 8,000, at least one radiation-hardenable functional group connects on it.The radiation-hardenable functional group can be connected on the hydrocarbon in any suitable mode, and for example, this paper is about the described person of polyester backbone.

The example of preferred hydrocarbon comprises the multipolymer of tygon, polybutylene, polypropylene and ethene, butylene and propylene.Also can use neoprene and polybutadiene polymers, preferred polychlorobutadiene and polybutadiene are complete hydrogenation persons.

Preferred viscosity adjustment oligomer is that number-average molecular weight is about 4500 poly-ethylidene butylidene acrylate.The commercial examples of this oligomer is Kraton L 1203 (Shell ChemicalCo.).

Consumption with viscosity adjustment oligomer of hydrocarbon main chain can be higher than the consumption that tradition contains the release agent of silicone and fluorine far away.Especially, this viscosity adjustment oligomer consumption can be preferably about 5～80wt% for about 1～about 90wt%, and more preferably about 10～about 70wt% is in the general assembly (TW) of radiation curable ink coating composition.

The main oligomer of viscosity adjustment oligomer as ink coating composition can be used.Yet, usually other radiation-hardenable oligomer and monomer are mixed with the viscosity adjustment oligomer, so that the performance of ink coating is met the requirements.Preferably, it is compatible with the viscosity adjustment oligomer to be chosen in the radiation-hardenable monomer and the oligomer that exist in the radiation-hardenable carrier system, so that the viscosity adjustment oligomer keeps dissolving or disperse state in liquid radiation-hardenable carrier system.The compatibility of monomer and oligomer and viscosity adjustment oligomer shown in following example, can easily be measured.Especially, the viscosity adjustment oligomer can mix with needed monomer and oligomer.If find the potpourri muddiness, monomer or oligomer are perhaps incompatible with the viscosity adjustment oligomer so.Yet, if desired, also can use the incompatible potpourri of monomer, oligomer and viscosity adjustment oligomer.But, before applying, perhaps must stir ink composite, so that disperse the viscosity adjustment oligomer.

Can be used for preparing again so that contain according to commercial examples viscosity adjustment oligomer of the present invention, that suit ink composite, comprise the UV curable printing ink that DSM Desotech company produces, it is based on the polyfunctional acrylic ester monomer.

Ink coating is about 3～about 10 micron thickness usually, and is normally concentric, in case the transmission signals decay.Yet, if desired, can apply ink coating in any form, but its formation should be suitable for offering each root coated optical glass fiber with recognizable color and luster.The example of suitable coating comprises dash line, dotted line, line and ring.Preferred ink coating is an essentially concentric.Can provide the ink coating of essentially concentric according to ink coating composition of the present invention, and discontinuous ink coating, for example: dash line, dotted line, line and ring.When apply be less than concentric coating the time, can utilize the viscosity adjustment oligomer matrix material with point, short draw or ink coating that alternate manner applies separates.

The Tg of ink coating generally also is at least about 50 ℃, more preferably at least about 70 ℃.Any one those of ordinary skill of preparation radiation curable ink compositions field knows how to regulate radiation-curable composition, so that needed solidified coating performance is provided.Therefore, be generally used for forming the radiation-hardenable composition of outer bottom coating composition, can prepare and in according to ink composite of the present invention, be used as the radiation-hardenable carrier system again.The example of the suitable radiation-hardenable composition that can prepare again by various features comprises, in US Patent No 4,624, and 994,4,682,851,4,782,129,4,794,133,4,806,574,4,849,462,5,219,896 and 5, in 336,563 disclosed those, all be hereby incorporated by.

Be suitable for forming the radiation-hardenable carrier system of ink composite of the present invention, contain one or more radiation-hardenable oligomer or monomers, it has the functional group that at least one can polymerization when being subjected to actinic radiation.Well-known now suitable radiation-hardenable oligomer or monomer, this belongs to the art technology scope.

Generally, employed radiation-hardenable functional group is an alkene class unsaturated group, and it can be through free radical polymerization or cationic polymerization polymerization.The instantiation of suitable alkene unsaturated group thing is to contain acrylate, methacrylate, the group of styrene, vinyl ether, vinyl acetate, N-substituted acrylamide, vinylamide, maleate and fumarate.Preferred alkene unsaturated group is provided by the group that contains acrylate, methacrylate or N-vinyl functional group.

The functional group of general other type of using by, for example, epoxy radicals, perhaps mercaptan-alkene or amine-alkene system provides.Epoxy radicals can be through the cationic polymerization polymerization, and mercaptan-alkene and amine-alkene system is usually through the Raolical polymerizable polymerization.Epoxy radicals can, for example, homopolymerization.In mercaptan-alkene and amine-alkene system, for example, polyreaction can occur in contain the undersaturated group of allyl and contain tertiary amine or the group of mercaptan between.

Preferably, the radiation-hardenable functional group who in oligomer, exists at least about 80mol%, be acrylate, methacrylate and N-vinyl more preferably at least about 90mol%.

Can use single functionality, two, three, four and the oligomer of high functionality more so that obtain needed performance balance.Wherein, functionality refers to the radiation-hardenable functional group's who exists number in oligomer.

Oligomer comprises bonding radiation-hardenable functional group's carbon containing backbone structure usually.The suitable example that contains carbon backbone chain comprises polyethers, polyolefin, polyester, polyamide and polycarbonate.Can select to contain the size of carbon backbone chain, so that needed molecular weight to be provided.That the number-average molecular weight of oligomer is generally is about 500～about 10,000, be preferably about 500～about 7,000, most preferably be about 1000～about 5,000.

For example, oligomer contains epoxy radicals or the alkoxy that carbon backbone chain can comprise aryl and open loop.Oligomer can be expressed as, for example:

R-Ar-R; Or

R-L-Ar-L-R

In the formula: r is the radiation-hardenable functional group,

Ar be contain this part aryl and

L connects base.

The example of suitable connection base comprises the epoxy radicals of alkoxy or open loop, for example ethoxy, propoxyl group, butoxy with and repetitive.L also can be that carbamate or urea connect base.

Aryl can, for example, derived from the bis-phenol unit, as bisphenol-A.Preferred oligomer is the diglycidyl ether derivant of the bisphenol-A of bonding acrylate-functional base.The commercial examples of this quasi-oligomer is CN-120 (Startomer), and its molecular weight is about 1300, and when solidified, Tg is about 65 ℃.

Another example of preferred oligomer be that molecular weight is about trifunctional polyethers or polyester of 500～about 5000.The example of preferred trifunctional oligomer be commercially available polycarbamate triacrylate Ebecryl 264, its molecular weight is about 2000, Tg is about 42 ℃ when solidified.

The radiation-hardenable carrier system also can contain the reactive diluent that is useful on adjusting viscosity.Reactive diluent can be the low viscosity monomer that contains the functional group that at least one can polymerization when being subjected to actinic radiation.Usually, the viscosity of low viscosity diluent monomer is about 50～about 500 centipoises in the time of 25 ℃.The example of the suitable viscosity of optical glass fibre coating composition is to be about 500～about 50,000 centipoises in the time of 25 ℃.This functional group can have identical character with the user of institute in radiation-hardenable monomer or oligomer.Preferably, the functional group who exists in reactive diluent can carry out copolymerization with the radiation-hardenable functional group who exists on radiation-hardenable monomer or oligomer.

For example, reactive diluent can be to contain acrylate or vinyl ether functional base and C ₄～C ₂₀The monomer of alkyl or polyether moiety or monomer mixture.The instantiation of this class reactive diluent comprises Hexyl 2-propenoate, 2-EHA, isobornyl acrylate, decyl acrylate, lauryl acrylate, acrylic acid stearyl, acrylic acid 2-ethoxy ethoxy-ethyl ester, lauryl vinyl ether, 2-ethylhexyl vinyl ether, N-vinyl formamide, isodecyl acrylate, acrylic acid isooctyl acid, caprolactam, vinyl pyrrolidone etc.

The another kind of reactive diluent that can use is the compound that contains aryl.The instantiation that contains the aryl reactive diluent comprises ethylene glycol phenyl ether-acrylate, polyglycol phenyl ether acrylate, polypropylene glycol phenyl ether-acrylate, the phenyl derivatives that replaces with the alkyl of above-mentioned monomer, for example polyethylene glycol nonylphenyl ether-acrylate.

Reactive diluent also can comprise and contains two or more thinning agents that can carry out the functional group of polyreaction.The object lesson of this class monomer comprises: C ₂～C ₁₈The diacrylate of hydrocarbon glycol, C ₄～C ₁₈Hydrocarbon divinyl ether, C ₃～C ₁₈Hydrocarbon triacrylate and polyether analogues thereof etc., for example, diacrylate 1,6-hexylene glycol ester, trimethyol propane triacrylate, hexanediol divinyl ether, two diacrylate and two of three (ethylene glycol) diacrylate, three acrylic acid isoamyl tetrol esters, ethoxylation bisphenol-A three (propylene glycol) diacrylate that contracts that contracts.

If the radiation-hardenable functional group of radiation-hardenable monomer or oligomer is an epoxy radicals, for example, one or more following compounds can be used as reactive diluent; 7-oxa-bicyclo[4.1.0, phenyl ethylene oxide, 1,2-epoxy-4-vinyl cyclohexane, glycidyl acrylate, 1, the diglycidyl ether of 2-epoxy-4-epoxy ethyl-cyclohexane, polyglycol, the diglycidyl ether of bisphenol-A etc.

If the radiation-hardenable functional group of radiation-hardenable monomer or oligomer contains amine-alkene or mercaptan-alkene system, the example of the reactive diluent that contains the allyl unsaturated group that can use so comprises: diallyl phthalate, trimellitic acid triallyl, trimerization triallyl cyanurate, trimerization triallyl isocyanurate and diallyl isophthalate.

For amine-alkene system, the amine official that can use can comprise by thinning agent, for example, the adduct of trimethylolpropane, isophorone diisocyanate and two (first) ehtylethanolamine, the adduct of hexanediol, isophorone-diisocyanate and dipropyl monoethanolamine, and the adduct of trimethylolpropane, trimethyl hexamethylene diisocyanate and two (first) ehtylethanolamine.

The radiation curable ink composition can contain the light trigger that generates free radical.The example of suitable radical photoinitiator includes, but not limited to following material: the isobutyl benzoin ether; 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide; 1-hydroxy-cyclohexyl phenyl ketone; 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-(1)-ketone; 2,2-dimethoxy-2-phenyl acetophenone; Perfluoro diphenyl two luxuriant titaniums; 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-(4-morpholinyl)-1-acetone; 2-hydroxy-2-methyl-1-phenyl third-1-ketone; 4-(2-hydroxy ethoxy) phenyl-2-hydroxyl-2-propyl ketone; The dimethoxy benzene benzoylformaldoxime; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone; 1-(4-dodecyl-phenyl)-2-hydroxy-2-methyl third-1-ketone; 4-(2-hydroxy ethoxy) phenyl-2-(2-hydroxyl-2-propyl group)-ketone; The diethoxybenzene benzoylformaldoxime; (2,6-dimethoxy benzoyl)-2,4, the potpourri of 4-tri-methyl-amyl phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-third-1-ketone; Benzophenone; 1-acetone, 2-methyl isophthalic acid-1-(4-(methyl mercapto) phenyl) 2-(4-morpholinyl); And composition thereof.

Other adjuvant that can be used in the radiation-hardenable carrier system comprises, but is not limited to catalyzer, lubricant, wetting agent, antioxidant and stabilizing agent.The selection of these adjuvants and use are among the art technology scope.

Coated optical fiber is in being commonly used in the fabric strip assembly.Because the multifunctionality of ink coating composition of the present invention, said composition are highly suitable on the coated optical glass fiber in the fabric strip assembly.Ink coating made in accordance with the present invention, can make us providing uncannily central span near and need not use release agent.Under not preferred situation, still can use release agent if desired.Suitable release agent comprises silicone, siloxane acrylate, carbon fluorocarbon oil or its resin etc.Because from seeing that by nature that central span can be provided is approaching,, can significantly reduce so the amount of the release agent that is added is compared with traditional ink coating according to ink coating of the present invention.The amount of release agent can be for about 0.1～about 5wt%, based on the ink composite general assembly (TW).

Can use any inorganic and organic pigment that is suitable for making the radiation curable ink composition in the present invention." pigment " refers to inorganic and organic pigment the term that uses.

Use the fabric strip assembly of the coated optical glass fiber below 12 or 12 only to need 12 kinds of color and lusters just to be enough to make every coated optical fiber to be distinguished from each other.Yet, in big fabric strip assembly, can use color more than 12 kinds, so that make coated optical glass fiber can access suitable differentiation to each other.That the example of making the normally used 12 kinds of colors of fabric strip assembly comprises is black, white, yellow, blue, red, green, orange, brown, pink, blue-green, purple and grey.

The instantiation of suitable black pigment comprises carbon black.

The instantiation of suitable Chinese white comprises titania.

The instantiation of suitable yellow uitramarine comprises the yellow and diazonium series pigments of diaryl thing.

The instantiation of suitable blue pigment comprises phthalocyanine blue, basic dye pigment, and phthalocyanine dye.

The instantiation of suitable red pigment comprises that anthraquinone (red), naphthol reds, monoazo series pigments, quinoline a word used for translation ketone pigment, anthraquinone, are with perylene.

The instantiation of suitable viridine green comprises phthalocyanine green and nitrose pigment.

The instantiation of suitable orange pigment comprises that monoazo and diazonium series pigments, quinoline a word used for translation ketone pigment, anthraquinone are with perylene.

The instantiation of suitable purple dye comprises quinoline a word used for translation ketone purple, basic dye pigment and carbazole dioxazine series pigments.

Suitable blue-green, brown, grey and pink pigment is by mixing other pigment can easily to prepare.Those skilled in the art can allot any color and luster by mixing different pigment on demand.

The amount of pigment that can exist in ink composite is to provide the macroscopic color that need not amplify to be beneficial to the discriminating of each root pigmented optical glass fibre.Amount of pigment should be not greatly decline to a great extent or causes other not wish the degree of the infringement that occurs to the solidification rate that makes ink composite.The example of having found the amount of pigment that suits is about 1～about 20wt%, is preferably about 1～about 15wt%, and more preferably about 1～about 10wt% is based on the ink composite general assembly (TW).

Based on above-mentioned, suitable radiation curable ink composition can be prepared from comprising following component:

At least a pigment of about 1～about 20wt%;

About 1～about 90wt% viscosity adjustment oligomer.

Preferred ink composite can be prepared from comprising following component:

At least a pigment of about 1～about 20wt%;

About 1～about 90wt% viscosity adjustment oligomer;

Optional about other radiation-hardenable oligomer of 1～about 80wt%;

At least a radiation-hardenable diluent monomer of about 1～about 80wt%.

The preferred amounts of other radiation-hardenable oligomer is about 10～about 70wt%, and more preferably about 20～about 60wt% is based on the general assembly (TW) of ink composite.

The preferred amounts of radiation-hardenable diluent monomer is about 5～about 70wt%, and more preferably about 10～about 60wt% is based on the general assembly (TW) of ink composite.

The amount of the light trigger that preferred ink compositions contains is about 1～about 20wt%, and more preferably about 1～about 10wt% is based on the general assembly (TW) of ink composite.

Ink coating composition can be applied on the coating optical glass, and adopt any suitable method to solidify.A kind of example of proper method is disclosed in US Patent No 4,629, and in 285, its whole disclosures are incorporated herein by reference at this paper.Ink composite also can with stretch at optical glass fibre and coating apparatus on apply outside the similar manner of undercoat apply.

Undercoat is used to replace ink coating outside colour, the perhaps place that is used in combination with ink coating, for example, when applied amount is less than concentric ink coating, apply for this type of, the viscosity adjustment oligomer can be mixed outside colour in the undercoat, so that outside colour, provide needed level of adhesion between undercoat and the matrix material.Based on the disclosure that this paper was provided, those skilled in the art can utilize the viscosity adjustment oligomer to prepare needed painted outer undercoat.For example: the radiation-hardenable foundational system of outer undercoat is similar to the radiation-hardenable carrier system of ink coating.Like this, the bond properties of outer undercoat can be regulated by adopting the viscosity adjustment oligomer with the method identical with ink coating described herein.The outer undercoat of traditional stains by sneaking into the viscosity adjustment oligomer therein, can become the improved painted outer undercoat according to the present invention.The example of suitable painted outer undercoat is disclosed among the PCT application WO 90/13579 that has delivered, is incorporated herein its whole disclosures as a reference.

Preferred viscosity adjustment oligomer amount is, the amount of the painted outer undercoat of (interface of outer undercoat and the matrix material) surface energy with following apical grafting feeler can be provided, promptly, greater than 65 °, preferably be equal to and greater than about 70 °, even more preferably be equal to and greater than about 75 °, and most preferably being equal to and greater than about 80 °, its condition is not use traditional compound that contains silicone and fluorine.

Also the viscosity adjustment oligomer can be sneaked in the composition of formation matrix of radiation-hardenable, but so that give the release property of formed matrix material from ink coating.The composition of the formation matrix of radiation-hardenable based on to employed similar radiation-hardenable monomer and oligomer in above-mentioned ink coating composition.Prepare the ratio of the viscosity adjustment oligomer of above-mentioned ink coating composition, can be used for preparing composition according to improved formation matrix of the present invention.Like this, those skilled in the art can easily make the composition of improved formation matrix, and the matrix material that said composition provided in the time of in being applied to the fabric strip assembly, always has central span near performance.The composition that can be formulated as the suitable formation matrix that comprises the viscosity adjustment oligomer again is disclosed in US Patent No 4,844,604, and its whole disclosures are hereby incorporated by.

Preferred viscosity adjustment oligomer amount is, the amount of the matrix material of the surface energy with following apical grafting feeler can be provided, promptly, greater than 65 °, more preferably be equal to and greater than about 70 °, even more preferably be equal to and greater than about 75 °, and most preferably being equal to and greater than about 80 °, its condition is not use traditional compound that contains silicone and fluorine.

The viscosity adjustment oligomer can be applied in the fabric strip assembly or ink coating in or in the matrix material, perhaps among both, so that the bond properties of ink coating and matrix material is met the demands.

The now well-known fabric strip assembly in this area, those skilled in the art can easily use disclosure provided herein, the fabric strip assembly that contains at least a improved ink coating optical glass fibre of preparation novelty by purposes.Tencel band assembly according to the present invention's preparation can be used in the telecommunication system.Described telecommunication system generally comprises fabric strip assembly, transmitter, receiving trap and the switch that contains optical glass fibre.The fabric strip assembly that contains coated optical glass fiber is the basic connection device of telecommunication system.It is underground or under water that the fabric strip assembly can be embedded in, and connects to realize long distance, such as between the city.The fabric strip assembly also can be used to be directly connected to the dwelling.

Tencel band assembly also can be used for cable television system made in accordance with the present invention.This cable television system generally includes fabric strip assembly, transmitter, receiving trap and the switch that contains optical glass fibre.The fabric strip assembly that contains coated optical glass fiber is the basic connection device of this cable television system.The fabric strip assembly can be grown distance and be embedded in undergroundly or under water, connects such as between the city to realize long distance.The fabric strip assembly also can be used to be directly connected to the dwelling.

Further explain the present invention by following example, but be not limited to this.

Example 1～13 and Comparative examples A

Ink composite forms when being used for the fabric strip assembly to have the approaching ability at the ink coating that does not use silicone and carbon fluorine class remover of central span and tests by the following stated.At first the component shown in the table 1 is mixed and form radiation-hardenable carrier base composition.Wherein two kinds of base compositions contain according to viscosity adjustment oligomer of the present invention (B-1 and B-2).

By pressing shown in the table 2 base composition and pigment are mixed, form the radiation curable ink coating composition.Whether the check ink coating composition can provide central span approaching.Test findings is shown in table 2.

Table 1

Component (wt% is based on the carrier system general assembly (TW))	The B-1 of carrier is carrier system	The B-2 of carrier is carrier system	The B-3 of carrier is carrier system
				Poly-(12-hydroxy stearic acid) urethane acrylate	22.72	?76.7	?0
Epoxy acrylate	20.84	?0	?38.6
				Six functional aromatic urethane acrylates	9.17	?0	?0
Aliphatic urethane triacrylate with hexanediol diacrylate dilution 15%	10.56	?0	?32.4
				Tetrapropylene acid isoamyl tetrol ester	11.59	?0	?10
Hexanediol diacrylate	18.29	?17.04	?1.51
				Troysol 98C surfactant (Troy)	0.57	?0	?0
2,6-di-t-butyl-methyl-phenol	0.57	?0.57	?0
				2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) fourth-1-ketone	1.14	?1.14	?0
2-methyl isophthalic acid-(4-(methyl mercapto) phenyl) 2-(4-morpholinyl) 1-acetone	4.55	?4.55	?0
				The siloxane diacrylate	0	?0	?1.21
50% phosphine oxide, diphenyl (2,4,6-trimethylbenzene formyl) and 50%2-hydroxyl-2-methyl isophthalic acid-phenyl-1-acetone	0	?0	?10
				Isobornyl acrylate	0	?0	?3
The acrylic acid phenoxy ethyl	0	?0	?3
				Hydroquinone monomethyl ether	0	?0	?0.14
Phenothiazine	0	?0	?0.14

Table 2

Component (wt% is based on composition total weight)	Example 1 is white	Example 2 is bluish grey	Example 3 indigo plants	Example 4 purples	Example 5 Huangs	Example 6 is pink	Example 7 oranges	Example 8 is green	Example 9 is brown	Example 10 blue-greens	Example 11 indigo plants	Example 12 is red	Example 13 oranges
														The B-1 of carrier is carrier system	?86.37	??88.5	????88	??83.77	??79.8	????83	????82	??85.5	??82.15	??84.68	????0	????0	????0
The B-2 of carrier is carrier system	?0	??0	????0	??0	??0	????0	????0	??0	??0	??0	????88	????78.14	????82
														Pigment	13.63	?11.5	????12	??16.23	??20.2	????17	????18	??14.5	??17.85	??15.32	????12	????21.86	????18
Test findings
														Central span is approaching	By	By	By	By	By	By	By	By	By	By	By	By	By
Outer undercoat	P1	?P1	????P1	??P1	??P1	????P1	????P1	??P1	??P1	??P1	????P1	????P1	????P1
														Matrix material	M1	?M1	????M1	??M1	??M1	????M1	????M1	??M1	??M1	??M1	????M1	????M1	????M1

The result proves shown in the table 2, can provide according to viscosity adjustment oligomer of the present invention to have the ink coating of central span near performance by nature.

Matrix material M1-M5

The below test explanation different matrix material influence approaching to central span.The composition that radiation-hardenable forms matrix by with component shown in the table 4 is mixed must.

Ink composite shown in the employing table 3 provides central span approaching ability with the method check matrix material identical with example 1.Test findings is shown in table 4.

Table 3

Component (wt% is with respect to general composition weight meter)	Ink composite IN-2
		The propylene oxide ester	????18.82
Six functional aromatic urethane acrylates	????10.58
		Aliphatic urethane triacrylate with hexanediol diacrylate dilution 15%	????18.74
Pentaerythritol tetracrylate	????13.38
		Hexanediol diacrylate	????4.08
Trysol 98C surfactant (Troy)	????0.4
		2,6-di-t-butyl-methyl-phenol	????0.4
2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) fourth-1-ketone	????0.8
		1-acetone, 2-methyl isophthalic acid-1-(4-(methyl mercapto) phenyl) 2-(4-morpholinyl)	????3.2
Pigment	????9.6
		Poly-(12-hydroxy stearic acid) acrylate	????20

Table 4

Component (wt% is based on composition total weight)	??M1	??M2	??M3	??M4	??M5
						Oligomer H-T-(Pluracol 2010) 0.9-(SynFAC 8017) 1.4-T-H	????55	??61.1	??68.24	????55	????55
Isobornyl acrylate	????3.9	??4.3	??0	????5	????3.9
						The propoxylation ethylene glycol diacrylate	????3.9	??4.3	??0	????5	????3.9
The diacrylate of ethoxylation bisphenol-A	????23	??25.5	??11	????29.7	????23
						1-hydroxy-cyclohexyl phenyl ketone	????4	??4.4	??3	????4	????4
Diethyl sulfide two (3,5-two-tertiary butyl-4-hydroxy hydrogenated cinnamate)	????.3	??0.4	??0.3	????0.3	????.3
						The epoxidized soybean oil acrylate	????10	??0	??0	????0	????0
Polyglycol (Carbowax PEG 300)	????0	??0	??0	????0	????10
						Caprolactam	????0	??0	??10	????0	????0
The acrylic acid phenoxy ethyl	????0	??0	??6.46	????0	????0
						Dimethyl silicone polymer	????0	??0	??0.3	????0.3	????0
Dimethyl silicone polymer (surfactant)	????0	??0	??0.7	????0.7	????0
						Test findings
Outer undercoat	????P1	??P1	??P1	????P1	????P1
						Central span is near (behind the ink composition IN-2 that makes up oil 4 hours)	By	By	By	By	By

Oligomer makes by following composition is reacted: H=hydroxy-ethyl acrylate T=toluene diisocyanate Pluracol 2010=polypropylene glycol, molecular weight is about 2000 (BASF) SynFAC8017=ethoxylation bisphenol-A glycol (Milliken)

Result in the table 4 proves, uses the viscosity adjustment oligomer to provide and has the approaching fabric strip assembly of central span.

Example 14～15

Below the different additive of test explanation in matrix material provides the influence of the approaching ability of central span to matrix material.Adjuvant shown in the table 5 is mixed mutually with the material that radiation-hardenable forms matrix.Determine the ability that provides central span approaching by the method identical with example 1, test findings is shown in table 5.

Table 5

Component (wt% is based on composition total weight)	Example 14	Example 15
			Matrix composition M4	????90	????90
Kemester?6000	????10	????0
			The epoxidized soybean oil acrylate	????0	????10
Test findings
			Outer undercoat	????P1	????P1
Ink coating composition	????IN-1	????IN-1
			Central span is near (carrying out at once after the ink composition IN-1 that makes up oil)	By	By

Example 16～17

Use component shown in the table 6, the viscosity adjustment oligomer is added in the ink composite.By the method identical with example 1, check is not used fluorine-containing and ink composite silicone release agent provides central span approaching ability.Test findings is shown in table 6.

Table 6

Component (wt% is based on composition total weight)	Example 16	Example 17
			Ink composite IN-1	????80	????80
Poly-ethylidene butylidene acrylate	????20	????0
			Cardolite?NC-547	????0	????20
Test findings
			Outer undercoat	????P1	????P1
Matrix material	????M1	????M1
			Central span is near (carrying out at once after the ink composition IN-1 that makes up oil)	By	By

Table 6 is the result prove, can make us providing central span approaching under the condition of not using the release agent that contains silicone and fluorine uncannily according to the release layer of formation oligomer of the present invention.

Surface energy, example and comparative example

Mensuration is used for the surface energy according to the radiation-hardenable carrier is carrier system of the ink coating of the present invention's formation and traditional ink coating.Test findings is shown in table 7.

Table 7

Sample	Average apical grafting feeler (°)
		The B2 of carrier is carrier system (76.7wt%12HSA)	????80+/-2
The B1 of carrier is carrier system (22.72wt%12HSA)	????78+/-2
		The B1 of carrier is carrier system (not containing 12HSA)	????65+/-2
Commercially available printing ink carrier is carrier (except the silicone)	????62+/-1

Table 7 is the result prove, the present invention under the condition of not using silicone or fluorine release agent, can make us significantly reducing uncannily the ink coating surface energy.Contact angle is big more, and surface energy is low more.

Test routine

Central span is approaching

With blade coating thickness is that the outer bottom coating composition of commercially available radiation-hardenable of 75 μ m is applied on Mylar (polyethylene terephthalate) sheet material, and is exposed to the 1J/cm of Fusion D lamp in nitrogen atmosphere ²Under the ultraviolet light, be cured, form the outer bottom coating film that solidifies.Form the coating of sample radiation curable ink composition on the outer bottom coating film that solidifies, blade coating thickness is 5～10 μ m.Adopt Fusion D lamp irradiation 1J/cm in air ²Ultraviolet light solidifies ink composite, forms the ink coating that solidifies.Make commercially available radiation-hardenable matrix composition coating on ink coating, blade coating thickness is 75 μ m.1J/cm by irradiation FusionD lamp in nitrogen atmosphere ²Ultraviolet light solidifies matrix composition, forms the matrix material that solidifies on ink coating.

Cut the about 1/4～about 1/2 inch bar of width down from prepared multilayer film.At an end of each bar, the part matrix material is separated from ink coating with knife.Separating part at matrix material applies acting force, and remaining matrix material is peeled away from ink coating.If remaining matrix material cleanly from ink coating separately, ink coating does not sustain damage and matrix material is regardless of and splits, and ink coating has just passed through central span near test so.

Surface energy

Adopt La Mu-Hart contact angle determination only to carry out contact angle determination by stopping the method for dripping.Water is as test liquid.The Gilmont micro syringe that the stainless steel syringe needle is equipped with in employing places drop (4～8 μ l) on the sample surfaces.Measure contact angle after one minute.Carry out contact angle determination in the drop both sides, to guarantee symmetry.The contact angle of each sample is all measured on two kinds of different films.Carrying out 5 times on every kind of film measures.For each sample, amount to and use 10 drops.Average gained result, and basis of calculation deviation.In each case, all measure advancing contact angle.

Measure the air China ink interface contact angle of film." top " is air China ink coating interface, and " end " be mylar/ ink coating interface.Air China ink interface is represented, usually matrix material is applied to the surface on the ink coating.

The sample ink film is to adopt 3mil Byrd blade coating device that transparent ink base-material blade coating is gone up preparation to Mylar.Scraping films adopts the D lamp with 2J/cm ²In nitrogen atmosphere, be cured.The top and bottom of each sample all is cured.From Mylar released part film, place on the microscope slide plate and measure.

The matrix film is prepared in the same way, and just it is with 1J/cm ²Only end face is cured.

Claims (30)

1. An optical glass fiber ribbon assembly, which has the function of endowing each coated optical glass fiber with a span approaching, and the fiber ribbon assembly comprises: Many coated optical glass fibers; and A matrix material that binds said plurality of coated optical glass fibers together, wherein at least one of said coated optical glass fibers comprises: Optical glass fiber; at least one coating on said optical glass fiber; an ink coating on said at least one coating formulated from a composition comprising; Viscosity-modifying oligomers containing at least one radiation-curable functional group bonded to a low surface energy backbone and which are substantially free of silicone and fluorine; said viscosity-modifying oligomers are present in an amount such that The surface energy of the ink coating is reduced to make the adhesion between the ink coating and the base material less than that between the ink coating and the at least one coating on the optical glass fiber The level of adhesion between. 2. A radiation curable ink coating composition suitable for forming ink coatings on optical glass fibers, formulated from a composition comprising: Viscosity-adjusting oligomers, which contain at least one radiation-curable functional group bonded to a low surface energy backbone, and which are substantially free of silicone and fluorine; The composition is present in an amount that reduces the surface energy of the ink coating formed. 3. A radiation curable ink coating composition suitable for forming ink coatings on optical glass fibers, formulated from a composition comprising: Viscosity-modulating oligomers, which contain at least one radiation-curable functional group bonded to a low surface energy backbone, and which are substantially free of silicone and fluorine; characterized in that the viscosity-modulating oligomer has a number-average molecular weight It is 1,000 to 8,000, and 5% to 40% of the number average molecular weight of the viscosity adjusting oligomer is composed of hydrocarbon side chains. 4. A radiation curable matrix material composition suitable for forming a matrix material for bonding coated optical glass fibers together, said matrix material composition being formulated from a composition comprising: Viscosity-adjusting oligomers, which contain at least one radiation-curable functional group bonded to a low surface energy backbone, and which are substantially free of silicone and fluorine; The surface energy of the formed matrix material is reduced in an amount present. 5. A radiation curable matrix material composition suitable for forming a matrix material for bonding coated optical glass fibers together, said matrix material composition being formulated from a composition comprising: Viscosity-modulating oligomers, which contain at least one radiation-curable functional group bonded to a low surface energy backbone, and which are substantially free of silicone and fluorine; characterized in that the viscosity-modulating oligomer has a number-average molecular weight It is 1,000 to 8,000, and 5% to 40% of the number average molecular weight of the viscosity adjusting oligomer is composed of hydrocarbon side chains. 6. A radiation curable pigmented outer primer coating composition suitable for forming a colored outer primer coating on optical glass fibers, formulated from a composition comprising: A tack-modifying oligomer comprising at least one radiation-curable functional group bonded to a low surface energy backbone and which is substantially free of silicone and fluorine; The coating composition is present in an amount that reduces the surface energy of the pigmented outer base coat. 7. A radiation curable pigmented outer primer coating composition suitable for forming a colored outer primer coating on optical glass fibers, formulated from a composition comprising: Viscosity-modulating oligomers, which contain at least one radiation-curable functional group bonded to a low surface energy backbone, and which are substantially free of silicone and fluorine; characterized in that the viscosity-modulating oligomer has a number-average molecular weight It is 1,000 to 8,000, and 5% to 40% of the number average molecular weight of the viscosity adjusting oligomer is composed of hydrocarbon side chains. 8. According to any one of claim 1 to 7, the fiber tape assembly, ink coating composition, base material composition, or colored outer primer coating composition, is characterized in that said viscosity adjusting oligomer comprises At least one substance represented by the following general formula, which is formed by the reaction of the components listed in the general formula: P-(BHCA) _m -IR (2); P-((BHCA) _m -A-(BHCA) _m -I) _n -R (3); and RI-((BHCA) _m -A-(BHCA) _m -I) _n -R (4). where BHCA is a branched and/or hydroxycarboxylic acid containing non-terminal hydroxy-functional groups that provide hydrocarbon side chains attached to the polyester backbone resulting from the reaction of the hydroxy-functional groups to form ester groups; I is a polyisocyanate compound; A is a polyol; P is a compound containing at least one hydroxyl functional group; R is a hydroxy functional compound containing a radiation curable functional group; n is from 1 to about 20, on average; and m ranges from 1 to about 50, on average. 9. According to any one of claim 1 to 7, the fiber tape assembly, ink coating composition, base material composition, or colored outer primer coating composition, is characterized in that said viscosity-adjusting oligomer comprises At least one substance represented by the following general formula, which is formed by the reaction of the components listed in the general formula: RI-((BHCA) _S -A-(BHCA) _V -I) _W -R (7) wherein R is a hydroxyl functional radiation curable compound; I is a polyisocyanate compound; BHCA is a hydroxycarboxylic acid, which is branched and/or contains non-terminal hydroxyl functional groups, which can provide carbon-containing side chains attached to the polyester backbone by reaction of the hydroxyl functional groups to form ester groups; A is a polyhydric alcohol; W ranges from 1 to about 20, on average; and S+V ranges from 4 to about 20, on average. 10. The fiber tape assembly, ink coating composition, base material composition, or colored outer primer coating composition according to claim 9, wherein BHCA is poly(12-hydroxystearic acid), and A is Diols represented by the general formula:

In the formula: H is a hydrogen atom; O is an oxygen atom; C is a carbon atom; and R ₁₁ and R ₁₂ are respectively H or hydrocarbon side chains containing 1 to 12 carbon atoms, provided that R ₁₁ and R ₁₂ are not all H. 11. According to any one fiber tape assembly, ink coating composition, base material composition or coloring outer base coating composition in the claim 1～7, it is characterized in that, said viscosity adjustment oligomer comprises At least one substance represented by the following general formula, which is formed by the reaction of the components listed in the general formula: HA-I-Poly(HSA)-I-HA (8) where: HA is hydroxyethyl acrylate, I is isophorone diisocyanate; and Poly(HSA) is represented by the following formula (9) It is characterized in that B+C=2 to about 20, on average. 12. The fiber tape assembly, ink coating composition, matrix material composition, or pigmented outer primer coating composition according to claim 11, characterized in that B+C is from about 5 to about 15, on average. 13. The fiber tape assembly, ink coating composition, base material composition, or colored outer primer coating composition according to any one of claims 1 to 7, wherein said viscosity-adjusting oligomer comprises At least one substance represented by the following general formula, which is formed by the reaction of the components listed in the general formula: RI-(A-(PAC-A) _t -IR (10); R-(PAC-A) _t -IR (11); and R-(PAC-(A-PAC) _t -R (12). In the formula: PAC is a polycarboxylic acid compound; I is a polyisocyanate compound; R is a hydroxyl functional radiation curable compound; A is a polyol; and t is 1 to about 20, on average, characterized in that at least one of the polycarboxylic acid or polyol is branched so as to provide a polyester backbone with carbon-containing side chains, or the polyol contains non-terminal groups Hydroxyl functionality, which provides a polyester backbone with carbon-containing side chains due to the reaction of the hydroxyl functionality with a carboxylic acid to form an ester functionality. 14. According to any one fiber tape assembly, ink coating composition, matrix material composition or coloring outer primer coating composition in the preceding claim, it is characterized in that, described viscosity adjusts oligomer to provide the Said ink coating, said base material or said pigmented outer primer coating are present in an amount having a surface energy exhibiting an average top contact angle of greater than 65°. 15. According to any one fiber tape assembly, ink coating composition, base material composition or coloring outer primer coating composition in the preceding claim, it is characterized in that, described viscosity adjusts oligomer to provide the The ink coating, the matrix material, or the pigmented outer base coating are present in an amount having a surface energy exhibiting an average top contact angle of at least 70°. 16. According to any one fiber tape assembly, ink coating composition, base material composition or coloring outer primer coating composition in the preceding claim, it is characterized in that, said viscosity adjusts oligomer to provide said The ink coating, the matrix material, or the pigmented outer base coating are present in an amount having a surface energy exhibiting an average top contact angle of at least 75°. 17. According to any one fiber ribbon assembly, ink coating composition, base material composition or coloring outer primer coating composition in the preceding claim, it is characterized in that, described viscosity adjusts oligomer to provide the The ink coating, the matrix material, or the pigmented outer base coating are present in an amount having a surface energy exhibiting an average top contact angle of at least 80°. 18. According to any one fiber tape assembly, ink coating composition, base material composition or coloring outer base coating composition in the claim 1～7, it is characterized in that, the viscosity adjustment oligomer is at least Contains radiation curable functional groups bonded to a hydrocarbon backbone. 19. According to any one fiber ribbon assembly, ink coating composition, base material composition or colored outer primer coating composition in the claim 1～7, it is characterized in that, the viscosity adjustment oligomer is at least Contains radiation curable functional groups bonded to a hydrocarbon backbone including homopolymers or copolymers of ethylene, butene or propylene. 20. A ribbon assembly according to any one of claims 1 and 8 to 19, characterized in that said ink coating composition is cured in the presence of air. 21. According to any one of the fiber tape assembly, ink coating composition, matrix material composition or coloring outer primer coating composition in the preceding claim, it is characterized in that the presence of said viscosity adjusting oligomer From about 1 to about 90 wt%, based on the total weight of the radiation curable composition. 22. According to any one of the fiber tape assembly, ink coating composition, matrix material composition or coloring outer primer coating composition in the preceding claim, it is characterized in that the presence of said viscosity adjusting oligomer From about 5 to about 80 wt%, based on the total weight of the radiation curable composition. 23. According to any one of the fiber tape assembly, ink coating composition, matrix material composition or coloring outer primer coating composition in the preceding claim, it is characterized in that the presence of said viscosity adjusting oligomer From about 10 to about 70 wt%, based on the total weight of the radiation curable composition. 24. according to claim 3, the ink coating composition of any one in 5 and 7, base material composition or coloring outer primer coating composition, it is characterized in that, the number average molecular weight of described viscosity adjustment oligomer At least 10% of is composed of hydrocarbon side chains. 25. according to claim 3, any one ink coating composition, base material composition or coloring outer primer coating composition in 5,7 and 24, it is characterized in that, the number of described viscosity adjustment oligomer At least 15% of the average molecular weight consists of hydrocarbon side chains. 26. according to claim 3,5,7,24 and 25 any one ink coating composition, base material composition or coloring outer base coating composition, it is characterized in that, described viscosity adjustment oligomer Less than 30% of the number-average molecular weight of the compound is composed of hydrocarbon side chains. 27. According to claim 3, 5, 7 and 24～26 any one ink coating composition, base material composition or coloring outer base coating composition, it is characterized in that, described viscosity adjustment oligomer Less than 20% of the number-average molecular weight of the compound is composed of hydrocarbon side chains. 28. According to claim 3,5,7 and 24～27 any one ink coating composition, base material composition or coloring outer primer coating composition, it is characterized in that, described hydrocarbon side chain comprises A lower alkyl group or an alkyl-substituted aryl group of 3 to 30 carbon atoms. 29. According to claim 3,5,7 and 24～28 any one ink coating composition, base material composition or coloring outer primer coating composition, it is characterized in that, described hydrocarbon side chain comprises A lower alkyl group or an alkyl-substituted aryl group of 5 to 20 carbon atoms. 30. according to claim 3,5,7 and 24～29 any one ink coating composition, base material composition or coloring outer primer coating composition, it is characterized in that, described hydrocarbon side chain along all The main chains are separated by a comb-like structure.