WO2008066112A1

WO2008066112A1 - Radiation curable resin composition

Info

Publication number: WO2008066112A1
Application number: PCT/JP2007/073052
Authority: WO
Inventors: Hiroshi Miyazawa; Hiroyuki Ishii; Takahiko Kurosawa
Original assignee: Jsr Corporation; Dsm Ip Assets B.V.
Priority date: 2006-11-29
Filing date: 2007-11-29
Publication date: 2008-06-05
Also published as: JP2008195920A

Abstract

Disclosed is a radiation curable resin composition having characteristics suitable for a cladding material for polymer-clad optical fibers, particularly having low refractive index, stable transparency, good coatability, adequate adhesion to the core layer, and excellent strength and flexibility. Specifically disclosed is a radiation curable resin composition which contains, when the total amount of the composition is taken as 100% by mass, (A) 20-65% by mass of an ethylenically unsaturated group-containing fluorine-containing copolymer, (B) 20-60% by mass of a 2-perfluoroalkylethyl (meth)acrylate having 11-18 carbon atoms, and (C) 10-35% bymass of a compound other than the component (A) and the component (B), which does not have an aromatic structure nor a polar group but has two or more ethylenically unsaturated groups.

Description

Specification

Radiation curable resin composition

Technical field

[0001] The present invention relates to a liquid curable resin composition for forming a cladding layer of a polymer-clad optical fiber.

Background art

[0002] As an information communication cable, an optical fiber suitable for high-capacity, high-speed digital signal communication is being widely used instead of a so-called electric wire made of a metal wire that has been conventionally used. Various types of optical fibers are known, depending on their structure and form. The most basic structure of optical fibers is a core layer made of glass, quartz, or transparent resin, and the core layer. The clad layer is provided in contact with the outer side, and the outer side of the clad layer is further provided with a polymer coating layer made of a radiation curable resin or the like. Of these, all-silica optical fibers are often used in which both the core layer and the cladding layer are made of quartz. The typical diameter of the optical fiber core wire is about 125 m when combined with the core layer of about 50 m and the cladding layer, and about 250 to 500 m when combined with the resin coating layer.

[0003] On the other hand, optical modules having various functions such as optical signal transmission 'reception' branching 'switching have been developed for various optical information communication, and the optical axes of these optical modules and optical fibers. It is known that connecting and aligning are important in suppressing attenuation of optical signals. The diameter of the core layer of a conventional optical fiber core is small as described above. Since it is difficult to align the optical axis when connecting to an optical module, an optical fiber core with a core diameter increased to about 200 m is used. ! /

[0004] Since an optical fiber core having such a large diameter typically has a cladding layer made of a curable transparent resin, a polymer-clad optical fiber (plastic-clad optical fiber or polymer Also called a clad fiber). As the curable transparent resin constituting the clad layer, an example using a fluorine-containing ultraviolet curable composition containing fluorine-containing urethane (meth) acrylate or fluorine-containing (meth) acrylate oligomer is known! /, Ru (patent document;! ~ 3). [0005] Further, among polymer clad optical fibers, a type having a core layer made of glass or quartz, a type having a hard polymer clad optical fiber and a core layer made of transparent resin is called a plastic fiber. A hard plastic clad optical fiber is used for communication over a relatively long distance because of its high optical transmission efficiency, and a plastic fiber is used for communication over a relatively short distance.

[0006] The curable transparent resin material used for the clad layer of such a polymer-clad optical fiber has a low refractive index and a stable transparency over time; for obtaining good coatability. Appropriate viscosity; excellent adhesion to the core layer; properties such as Young's modulus, strength at break, strength represented by elongation at break, and flexibility

[0007] However, the resin material used for the clad layer of the conventional polymer clad optical fiber has a low refractive index and transparency, good coatability, adhesion to the core layer, strength 'polymer clad with excellent flexibility There is a problem that it is difficult to obtain a layer, and in particular, it is difficult to obtain a polymer clad layer having stable transparency even when the polymer clad optical fiber is left in a high temperature environment.

Patent Document 1: Japanese Patent Laid-Open No. 10-10340

Patent Document 2: Japanese Patent Laid-Open No. 10-160947

Patent Document 3: Japanese Patent Laid-Open No. 11-119036

Disclosure of the invention

Problems to be solved by the invention

[0008] The object of the present invention is to provide properties suitable as a clad material for polymer clad optical fibers, in particular, low refractive index and stable transparency, good coatability, adhesion to the core layer, strength 'flexibility' It is in providing the radiation-curable resin composition excellent in the.

Means for solving the problem

[0009] Therefore, the present inventor uses a radiation-curable resin composition comprising a specific fluorine-containing polymer, a specific fluorine-containing (meth) atrelate monomer, and a (meth) acrylate monomer having a specific structure not containing fluorine as essential requirements. And found that this purpose can be achieved.

That is, in the present invention, the total amount of the composition is 100% by mass, (A) 20 to 65% by mass of an ethylenically unsaturated group-containing fluorine-containing copolymer,

(B) 20 to 60% by mass of 2-perfluoroalkylethyl (meth) atalylate having 1 to 18 carbon atoms;

(C) 10 to 35% by mass of a compound other than the component (A) and the component (B), which does not have an aromatic structure and a polar group and has two or more ethylenically unsaturated groups

The radiation curable resin composition to be contained is provided.

The invention's effect

[0011] The polymer clad layer obtained from the resin composition of the present invention is particularly excellent in a low refractive index and stable transparency, good coatability, adhesion to the core layer, strength and flexibility.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] (A) Ethylenically unsaturated group-containing fluoropolymer:

The ethylenically unsaturated group-containing fluorine-containing polymer (A) is not particularly limited as long as it is a polymer having an ethylenically unsaturated group and a fluorine atom, but the fluorine-containing polymer having an ethylenically unsaturated group in the side chain. Olefin-based copolymers are preferred. By the component (A), the composition of the present invention exhibits basic performance as a clad forming material for polymer clad optical fibers such as low refractive index, high mechanical strength, and adhesion to a core layer such as glass or quartz.

[0013] The ethylenically unsaturated group-containing fluoropolymer is obtained by reacting the compound containing an ethylenically unsaturated group and an isocyanate group described below with the hydroxyl group of the hydroxyl group-containing fluoropolymer.

[1] A compound containing an ethylenically unsaturated group and an isocyanate group:

The compound containing an ethylenically unsaturated group and an isocyanate group is not particularly limited as long as it is a compound containing at least one ethylenically unsaturated group and at least one isocyanate group in the molecule. It is not something.

Moreover, since the curable resin composition mentioned later can be hardened | cured more easily as said ethylenically unsaturated group, the compound which has a (meth) atalyloyl group is more preferable. Examples of such compounds include (meth) acrylic acid, (meth) atari mouth alkylide, anhydrous (meth) acrylic acid, 2- (meth) ataryl oxychetyl isocyanate, 2- (meth) atariloy A single type of vanate or a combination of two or more types.

In addition, as a commercial item of (meth) atalylate having an isocyanate group, for example, trade name lenses MOI, AOI, BEI and the like manufactured by Showa Denko KK can be mentioned.

[0015] Further, such a compound can also be cF Fl I synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.

RCFIIate, xylylene diisocyanate, methylenebis (4-cyclohexylenoisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane are preferred.

[0016] As examples of the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferred! /.

In addition, as a commercial item of a hydroxyl group-containing polyfunctional (meth) atalylate, for example, Osaka Organic Chemical Co., Ltd., trade name HEA; Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA, PET-30; Product name Alonix M-215, M-233, M-305, M-400, etc.

(2) Hydroxyl group-containing fluoropolymer:

The hydroxyl group-containing fluoropolymer preferably contains the following structural units (a), (b) and ().

(a) A structural unit represented by the following formula (1).

(b) A structural unit represented by the following formula (2).

(c ′) A structural unit represented by the following formula (7).

[Chemical 1

(1)

[Wherein R ¹ represents a fluorine atom, a fluoroalkyl group or a group represented by OR ² (R ² represents an alkyl group or a fluoroalkyl group)]

[Chemical 2]

[Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, — (CH ₂ ) —OR ⁵ or OCOR ⁵ represents a group HHCII (R ⁵ represents an alkyl group or a glycidyl group) X is 0 or 1

ROCCIII

A number), a carboxyl group or an alkoxycarbonyl group]

[Chemical 3

11

― (7)

¾) _v OR ¹²

[Wherein R ^u represents a hydrogen atom or a methyl group, R ¹² represents a hydrogen atom or a hydroxyalkyl group, and V represents a number of 0 or 1]

[0018] (i) Structural unit (a):

In the above formula (1), the fluoroalkyl group of R ¹ and R ² includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorohexyl. And a fluoroalkyl group having 1 to 6 carbon atoms such as a perfluorocyclohexyl group. Examples of the alkyl group for R ² include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group.

The structural unit (a) can be introduced by using a fluorine-containing butyl monomer as a polymerization component. Such a fluorine-containing butyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples thereof include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; (Metino Levinino Leetenore), Novoleo Mouth (Echnolevininore Ete Nore), Novoleo Mouth (Propino Levinino Leete Nore). Perfluoro (alkyl butyl ether) such as (isobutyl butyl ether); Perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl butyl ether) may be used alone or in combination of two or more.

Of these, hexafluoropropylene and perfluoro (alkyl butyl ether) or perfluoro (alkoxy alkyl butyl ether) are more preferred and used in combination!

[0020] The content of the structural unit (a), the total amount of the structural units of the hydroxyl group-containing fluoropolymer in (a) ~ (c ') is 100 mol ^_0/0, 20 and 70 mol ^_0/0. This is because when the content is less than 20 mol%, it may be difficult to develop a low refractive index, which is an optically fluorine-containing material characteristic of the present invention. If the content exceeds 70 mol%, the solubility, transparency, or adhesion to the substrate of the hydroxyl group-containing fluoropolymer may decrease.

Moreover, such a reason, the content of the structural units (a), with respect to the total weight of the hydroxyl group-containing fluoropolymer, more preferably tool 30-60 mole to a 25 to 65 mole ^_0/0 force to the ^_0/0 S more preferred.

[0021] (ii) Structural unit (b):

In the formula (2), examples of the alkyl group of R ⁴ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group, Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

[0022] The structural unit (b) can be introduced by using the above-mentioned butyl monomer having a substituent as a polymerization component. Examples of such bur monomers include methyl buule tenole, ethino levinino ree tenole, n-propino levino ree tenole, isopropino levino ree tenole, n-butyl butyl ether, isobutyl butyl ether. Tert-Butyl bininore etherenole, n-pentinorevininoreethenore, n-hexinorevininoreethenore, n-octinorevininoreethenore, n-dodecinorevininoreethenore, 2-ethinorehexino Anolequinolevinoleatenore such as revininorenotere, cyclohexenorevininoreteorenore or cycloanol kirbüll ethers; such as ethyl ether, butylaryl ether, etc. Monotells; carboxylic acid bisesters such as butyl acetate, butyl propionate, butyl butyrate, bivalinate, valproate, versatic butyl and stearate; methyl (meth) acrylate and ethyl (meta ) Atalylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) (Meth) acrylic acid esters such as acrylate, etc .; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other unsaturated carboxylic acids, etc., alone or in combination of two or more .

[0023] The content of the structural unit (b) is 10 to 70 mol% when the total amount of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer is 100 mol%. It is. The reason for this is that when the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, when the content exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluorine-containing polymer may deteriorate.

Moreover, such a reason, the content of the structural units (b), with respect to the total weight of the hydroxyl group-containing fluoropolymer, preferably from the force S 20 to 60 mole ^_0/0, 30 to 60 mol force to the ^_0/0 S more preferred.

[Iii] (iii) Structural unit (c ′):

In the formula (7), the hydroxyalkyl group of R ¹² includes 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group. Group, 6-hydroxyhexyl group and the like.

[0025] The structural unit (c ') can be introduced by using a hydroxyl group-containing bull monomer as a polymerization component. Examples of such hydroxyl-containing bur monomers include 2-hydroxyethylenovininoleetenore, 3-hydroxypropinorevininoleetenore, 2-hydroxypropinorevininoreetenore, 4-hydroxybutinolebi Hydroxyl-containing butyl ethers such as Ninoreethenore, 3-Hydroxybutinorevininore Ethenore, 5-Hydroxypentinorevininoreetenore, 6-Hydroxyhexinorevininore Iter, 2-Hydroxyethylaryl ether, Examples include hydroxyl-containing aryl ethers such as 4-hydroxybutyl aryl ether and glycerol monoallyl ether, and aryl alcohol. In addition to the above, 2-hydroxyethyl (metatalylate, force prolatatatone (meth) atalylate, polypropylene glycol (meth) atrelate, etc.) can also be used as the hydroxyl group-containing butyl monomer.

[0026] The content of the structural unit (c ') is 5 to 70 monolayers when the total amount of the structural units (a) to (c') in the hydroxyl group-containing fluoropolymer is 100 mol%. % S is preferable. The reason for this is that when the content rate is less than ¾ mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be lowered, whereas when the content rate exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxy group-containing fluoropolymer may be deteriorated.

Moreover, such a reason, the content of the structural units (c '), with respect to the total weight of the hydroxyl group-containing fluoropolymer, preferably from the force S 5 to 40 mole ^_0/0, 5-30 Even more preferably the molar ^_0/0.

[0027] (iv) Structural unit (d) and structural unit (e):

The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).

[0028] (d) A structural unit represented by the following formula (6).

[Chemical 4

[Wherein R ⁹ and R ^1Q represent the same or different hydrogen atom, alkyl group, halogenated alkyl group or aryl group]

[0029] In the formula (6), the alkyl groups of R ⁹ and R ^1Q include an alkyl group strength S having 1 to 3 carbon atoms such as a methylol group, an ethyl group, a propyl group, and a halogenated alkyl group. As trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, etc., C1-C4 fluoroalkyl group isotropic S, and aryl group as phenyl group, benzyl group, Examples thereof include a naphthyl group. The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (1). An example of such an azo group-containing polysiloxane compound is a compound represented by the following formula (8).

[Chemical 5] (§)

[Wherein R ″ to R ^lb represent the same or different hydrogen atom, alkyl group or cyan group, and R ^{17 to} R ² ° represent the same or different hydrogen atom or alkyl group. P, q is the number !! ~ 6, r, s is the number 0 ~ 6, t is the number !! ~ 200, u is the number !! ~ 20]

[0031] When the compound represented by the formula (8) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).

[0032] (e) A structural unit represented by the following formula (9).

[Chemical 6]

_R 14 _{Rl 7 R} 18 _R 13

I I I I

-C— (CH ₂ ) _q CONH (CH ₂ ) — Si— (OSi) _t (CH ₂ ) _s HOC (CH ₂ ) ^-C—

(9)

R ¹⁶ R ¹⁹ i ² . R ¹⁵

[Wherein R ″ to R ^lb , R ″ to R ^U , p, q, r, s, and t are the same as the above formula (8)]

[0033] In the formulas (8) and (9), the alkyl group represented by R ^{13 to} R ^{16 is} an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, etc. R ^{17 to} R ² ° alkyl groups include carbon groups such as methyl, ethyl, and propyl groups.

˜3 alkyl groups.

In the present invention, the azo group-containing polysiloxane compound represented by the above formula (8) is particularly preferably a compound represented by the following formula (10).

[Chemical 7]

HO—- OC (CH ₂ ) ₂ — (JQ)

[Wherein t and u are the same as in the above formula (8)]

[0035] The content of the structural unit (d) is the total amount of the structural units of the hydroxyl group-containing fluoropolymer in (a) ~ (c ') is 100 mol ^_0/0, 0 .; ! preferable to be to 10 mol ^_0/0. The reason for this is that when the content is less than 0.1 mol%, the surface slipperiness of the coating after curing may be reduced, and the scratch resistance of the coating may be reduced. If it exceeds 10 mol%, the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling or the like may easily occur during coating.

Moreover, such a reason, the content of the structural units (d), with respect to the total weight of the hydroxyl group-containing fluoropolymer, 0;.! ~ 5 mol ^_0/0 and more preferred to implement 0 .;! the force S further preferred and to 3 mol ^_0/0. For the same reason, it is desirable that the content of the structural unit (e) should be determined so that the content of the structural unit (d) contained therein falls within the above range.

[0036] (V) Structural unit (f):

The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit ω.

[0037] (f) A structural unit represented by the following formula (11).

[Chemical 8

[Wherein, R ^Z1 is a group represented by the following formula (12).

[Chemical 9

η ~ OCH ₂ CH (OCH ₂ CH ₂ ) OH (12)

[Where n is a number from! To 20; m is a number from 0 to 4; k is a number from 3 to 50]

The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following formula (13). Yes

[Chemical 10]

[Wherein n, m and k are the same as in the above formula (12)]

[0039] The content of the structural unit (f) is the total amount of the structural units of the hydroxyl group-containing fluoropolymer in (a) ~ (c ') is 100 mol ^_0/0, 0,; ! preferable to be to 5 mol ^_0/0. The reason for this is that when the content is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. On the other hand, when the content is within 5 mol%, the curable resin composition is used. This is because the adhesiveness of the film does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material.

Moreover, such a reason, the content of the structural unit (f), with respect to the total weight of the hydroxyl group-containing fluoropolymer, 0.1;! ~ 3 mole ^_0/0 and more preferred to implement 0 . force for the 2-3 mole ^_0/0 S more preferred.

[0040] (3) Ethylenically unsaturated group-containing fluoropolymer:

The (A) component ethylenically unsaturated group-containing fluoropolymer has a compound containing a hydroxyl group, an ethylenically unsaturated group, and an isocyanate group contained in the structural unit (c ′) of the hydroxyl group-containing fluoropolymer. It can be obtained by reacting with a reactive group such as an isocyanate group. In this case, the molar ratio of the isocyanate group of the compound containing the ethylenically unsaturated group and the isocyanate group to the hydroxyl group of the hydroxyl group-containing fluoropolymer is 1.;! It is preferable to use a ratio.

[0041] Therefore, (A) the ethylenically unsaturated group-containing fluorine-containing polymer is a hydroxyl group-containing fluorine-containing polymer in addition to the structural unit (a) and the structural unit (b) derived from the hydroxyl group-containing fluorine-containing polymer. The structural unit (c ′) has the following structural unit (c) produced by reacting with a compound containing an ethylenically unsaturated group and an isocyanate group. When the hydroxyl group-containing fluoropolymer has the structural unit (d), structural unit (e), structural unit (f), etc., these structural units are composed of an ethylenically unsaturated group and an isocyanate group. Do not react with compounds containing Therefore, (A) the ethylenically unsaturated group-containing fluoropolymer also has the structural unit (d), the structural unit (e), the structural unit ω and the like.

Structural unit (c);

[Chemical 11]

HHCII

RCOCIII 6

(3)

H ₂ ) _v OR ⁷

[Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a group represented by the following formula (4) or (5), and V represents a number of 0 or 1

[Chemical 12]

R ⁸

— CN— (CH ₂ ) ₂ 0-CC = CH _{2 (4} )

o o

(In the formulas (4) and (5), R ⁸ represents a hydrogen atom or a methyl group)]

The molecular weight of the ethylenically unsaturated group-containing fluorine-containing copolymer should be 5,000-500,000 as the number average molecular weight in terms of polystyrene measured with tetrahydrofuran as a solvent by gel permeation chromatography (GPC). preferable. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the cured product may be lowered. On the other hand, when the number average molecular weight exceeds 500,000, the viscosity of the composition is decreased. This is because there is a case where coating becomes difficult and the coating becomes difficult.

For these reasons, the ethylenically unsaturated group-containing fluorine-containing copolymer preferably has a polystyrene-equivalent number average molecular weight of 10,000 to 300,000, and is preferably 10,000 to 100,000. More preferably. [0043] The ethylenically unsaturated group-containing fluorine-containing copolymer as the component (A) is usually compounded in an amount of 20 to 65% by mass, preferably 20 to 50% by mass, based on the total amount of the composition. Particularly preferably, 30 to 40% by mass is blended. If it is less than 20% by mass, the refractive index of the cured product will increase, and the adhesion to the core layer tends to decrease. If it exceeds 65% by mass, the blending amount of component (B) and component (C) will be reduced. As a result, the solubility of the component (A) may decrease, and it may be difficult to obtain a highly transparent cured product.

(B) 2-perfluoroalkylethyl (meth) acrylate having 1 to 18 carbon atoms: Component (B) blended in the composition of the present invention has 11 carbon atoms. It is 2-perfluoro oral alkyl ethyl (meth) acrylate which is ~ 18, and is usually represented by the following formula (14).

CH = CHCOOCH CH (CF) F (14)

[Wherein n represents 6 to; 12 represents a number]

The component (B) is blended together with the component (C) described later in order to reduce the refractive index of the cured product, in addition to the purpose of ensuring the solubility of the component (A). Among these, 2-perfluorooctylethyl (meth) acrylate is preferable because it is suitable for dissolving the component (A) and is easily available.

[0045] The component (B), 2-perfluoroalkylethyl (meth) acrylate, is usually added in an amount of 20 to 60% by mass, preferably 25 to 60% by mass, based on the total amount of the composition. It is particularly preferably 40 to 50% by mass. If it is less than 20% by mass, the solubility of the component (A) may be impaired, and the refractive index of the cured product may be reduced. If it exceeds 70% by mass, the viscosity of the composition will be reduced and the coating property will be reduced. Is damaged.

[0046] The compatibility between the (A) component ethylenically unsaturated group-containing fluorine-containing copolymer and the (meth) acrylate monomer is often limited. By mixing with the combination of components C), the solubility is improved and a uniform composition can be obtained. In particular, the mixing ratio of the component (B) and the component (C) is preferably 2: 3 to 5: 1 as a mass ratio, more preferably 2: 3 to 4: 1.

[0047] (C) Compound having no aromatic structure and no polar group and having two or more ethylenically unsaturated groups:

Component (C) blended in the composition of the present invention does not have an aromatic structure and a polar group, and It is a compound having two or more tyrenically unsaturated groups. Since the component (C) does not have a polar group, when used in combination with the component (B), the solubility of the component (A) is increased to give a uniform composition. Further, since the component (C) does not have an aromatic structure, a cured product having a low refractive index is given.

Here, the polar group includes dissociable groups such as a carboxyl group and an amino group, and polarizable groups such as a carbonyl group and an alkylene oxide group having 3 or less carbon atoms, but a hydroxyl group is excluded. The component (C) is not particularly limited as long as it has a structure that satisfies the above requirements.

[0048] Specific examples of the component (C) include, for example, neopentyl dalycol di (meth) acrylate, neopentyl glycol hydroxybivalate di (meth) acrylate, trimethylol propane tri (meth) acrylate. , Trimethylolpropane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, 1, 4-butanediol di (meta) ) Aliphatic structure-containing (meth) acrylates such as acrylate and 1,6-hexanediol di (meth) acrylate.

[0049] Among the above-mentioned components (C), neopentyl glycol di (meth) acrylate or neopentyl glycol recall hydroxybivaline in which monofunctional or polyfunctional aliphatic structure-containing (meth) acrylate is preferred Acid ester di (meth) acrylate is particularly preferred. As the component (C), one type may be used alone, or two or more types may be used in combination.

[0050] The component (C) is usually blended in an amount of 10 to 35% by mass, preferably 15 to 35% by mass, particularly preferably 15 to 30% by mass, based on the total amount of the composition. If it is less than 10% by mass, the solubility of component (A) may be impaired, and if it exceeds 35% by mass, the blending amount of component (A) and component (B) will be reduced, resulting in refraction of the cured product. The rate increases and the adhesion to the core layer is impaired.

[0051] The composition of the present invention may further contain (D) (meth) acrylic acid or a dimer thereof. By blending component (D), the adhesion between the core layer, particularly the core layer made of glass or quartz, and the clad layer can be improved.

[0052] The component (D) is usually 0 to 10% by mass, preferably 1 to 7% by mass, based on the total amount of the composition. If it exceeds 10% by mass, the storage stability of the composition may be impaired. [0053] When the composition of the present invention is cured by irradiation with light such as ultraviolet rays, it is desirable to add (E) a photopolymerization initiator.

[0054] (E) Specific examples of the photopolymerization initiator include, for example, 1-hydroxycyclohexylphenylenoketone, 2,2-dimethoxy-1-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, Anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-clobenbenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-aminoaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin chinoleatenore , Penzino Resimethino Leketanol, 1- (4-Isopropinorefenenole) -2-Hydoxy-2-methylpropane 1-one, 2-Hydroxy-1-methyl-1-phenyl Pane 1-on, Thioxanthone, Jetylthioxanthone, 2-Isopropylthioxanth 2 Chloroxanthone, 2 Methyl-1 [4 (Methylthio) phenyl] -2 Morpholinopropane 1 ON, 2, 4, 6 Trimethylbenzoyldiphenylphosphine oxide, Bis (2, 6 dimethoxybenzoyl) 2, 4, 4 Trimethylpentyl Nolfoffinoxide; IRGACURE184, 369, 651, 500, 907, CGI1700, CG 11750, CGI1850, CG24-61; Darocure 1116, 1173 LucirinTPO (manufactured by BASF); ubeitalyl P36 (manufactured by UCB) and the like.

[0055] (E) When a photopolymerization initiator is used, a photosensitizer can also be used in combination. Examples of photosensitizers include triethylamine, jetylamine, N-methyljetanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate; 103, 104, 105 (above, manufactured by UCB). In addition, when the liquid curable resin composition of the present invention is cured by using heat and ultraviolet rays in combination, the thermal polymerization initiator and the photopolymerization initiator can be used in combination.

[0056] (E) The polymerization initiator is preferably blended in an amount of 0.;! To 10% by mass, particularly 0.3 to 7% by mass, based on the total amount of the composition.

[0057] The composition of the present invention does not have an aromatic structure and a polar group other than the components (F) (A), (B) and (C) as long as the effects of the invention are not impaired. 1 ethylenically unsaturated group Individual compounds can be blended.

Specific examples of such a compound having no aromatic structure and polar group and having one ethylenically unsaturated group include a bull group-containing ratatam such as N-bullpyrrolidone and N-bull force prolatatum;

Vinylinoatenoles such as hydroxybutinorevininoreethenore, laurinorevininoreethenore, cetinolevininoreethenore, 2-ethenorehexinorevininoreethenore; ru (meth) acrylamide, N, N-dimethyl Acrylamides such as aminopropyl (meth) acrylamide t-octyl (meth) acrylamide;

Contains alicyclic structures such as isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate (Meta) Atarirate;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) Atalylate, hexyl (meth) attarelate, 2-ethyl hexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, laurinore (meth) atelate, stearino ret (meta) ateari Rate, isosteari nore (meth) atarylate, tetra Contains aliphatic structures such as hydrofurfurinole (meth) acrylate, butoxychetyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate (meta

) Atarirate.

[0058] Component (F) is a power that is usually added in an amount of 0 to 30% by mass, preferably 0, based on the total amount of the composition

-25% by mass, particularly preferably 0-20% by mass. If it exceeds 30% by mass, the transparency of the composition and its cured product may be impaired.

[0059] The composition of the present invention includes (G) (A) component, (B) component, as long as the effects of the invention are not impaired. It is possible to add a compound having an ethylenically unsaturated group other than the components (C) and (F). Examples of the component (G) include aromatic structure-containing (meth) acrylate, polar group-containing (meth) acrylate, such as a carboxyl group and an alkylene oxide structure, and the like. The component (G) has a tendency to increase the refractive index of the cured product, as in the case of the aromatic structure-containing (meth) acrylate, and the solubility of the component (A) like the polar group-containing (meth) acrylate. Since the total amount of the composition is 100% by mass, the amount of component (G) is preferably 5% by mass or less.

[0060] Commercially available products of these components (G) include, for example, Upimer UV, SA1002 (above, manufactured by Mitsubishi Chemical Corporation), Alonix M-215, M-315, M-325 (above, manufactured by Toagosei Co., Ltd.), Sartoma I can mention CN4000 (Cartoma Co., Inc.), Aronix TO-1210 (Toago Gosei Co., Ltd.), etc.

[0061] In the composition of the present invention, various additives, for example, an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, and a silane coupling agent are added to the composition of the present invention as necessary, as long as the characteristics of the present invention are not impaired. , Thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, solvents, fillers, anti-aging agents, wettability improvers, coating surface improvers, etc. .

[0062] The viscosity of the composition of the present invention is preferably 0.8 to 5. OPa's at 25 ° C, and particularly preferably 1.5 to 6 Pa's.

[0063] It should be noted that the liquid curable resin composition of the present invention may be used in combination with heat curing in addition to force radiation curing by radiation. Here, the radiation means infrared rays, visible rays, ultraviolet rays, X-rays, electron rays, α rays, / 3 rays, γ rays, and the like.

[0064] The cured product of the liquid curable yarn and composite of the present invention preferably exhibits a yang ratio of 200 MPa to 500 MPa. In order to form an upjacket layer, it is preferable to coat the film to a thickness of 100 to 350 μm. Furthermore, a cable layer made of a thermoplastic resin can be provided in contact with the outside of the optical fiber upjacket layer.

Example

Next, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples.

Production Example 1 (Synthesis of hydroxyl-containing fluorine-containing copolymer) After fully replacing the stainless steel autoclave with an electromagnetic stirrer with an internal volume of 2.0 L with nitrogen gas, 400 g of ethynole acetate, 53. Hydroxyethyl butyl ether (HEVE) 44. Og, lauroyl peroxide 100 g, azo group-containing polydimethylsiloxane represented by the above formula (10) (VPS 1001, manufactured by Wako Pure Chemical Industries, Ltd.) 6. Og and Nonionic reactive emulsifier (NE 30, manufactured by Asahi Denka Kogyo Co., Ltd.) 20 · Og was charged, cooled to 50 ° C with dry ice methanol, and oxygen in the system was removed again with nitrogen gas.

Next, 120.0 g of hexafluoropropylene (HFP) was charged, and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C was 5.3 X 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours, and when the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was discharged and the autoclave was opened to obtain a polymer solution having a solid content concentration of 26.4%. The obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer. This is designated as “hydroxy group-containing fluoropolymer 1”.

The obtained hydroxyl group-containing fluoropolymer 1 was measured for a polystyrene-reduced number average molecular weight by GPC, which was about 70,000. Further, from the measurement results of fluorine content by the alizarin complexone method, both NMR analysis results of 'H-NMR and ¹³ c NMR, and elemental analysis results, each monomer constituting the hydroxyl group-containing fluoropolymer 1 was determined. When the ratio of the components was determined, the structural unit derived from hexafluoropropylene (structural unit (a)), the structural unit derived from perfluoro (propyl butyl ether) (structural unit (a)), and derived from ethyl bulle ether. The structural unit (structural unit (b)), a structural unit derived from hydroxyethyl butyl ether (structural unit (c ′)), the total amount of structural units (a) to (c ′) is 100 mol%. They were 25: 25: 25: 25 monole% respectively.

Production Example 2 ((A) Synthesis of fluorine-containing copolymer containing ethylenically unsaturated groups)

In a 1 liter separable flask equipped with a magnetic stirrer, glass cooling tube and thermometer, 41.0 g of the hydroxyl group-containing fluoropolymer 1 obtained in Production Example 1 was used as a polymerization inhibitor, 2, 6 G Butylmethylphenol 0.01 g, 2 perfluoro as diluent Octylethyl (meth) atarylate 41 · Og and neopentylglycol di (meth) atalylate 17. Og is charged, and the hydroxyl-containing fluoropolymer 1 dissolves at 50 ° C, making the solution transparent and uniform. Stir until.

Next, 0-90 g of 2-methacryloyloxychetyl isocyanate was added to this system and stirred until the solution was uniform, then 0.015 g of dibutyltin dilaurate was added to start the reaction, By maintaining the temperature of the system at 55 to 65 ° C and continuing stirring for 5 hours, an ethylenically unsaturated group-containing fluoropolymer was obtained. The obtained ethylenically unsaturated group-containing fluorine-containing polymer is referred to as “ethylenically unsaturated group-containing fluoropolymer 1”. The dilution solvent used at this time can be used as a component of the ultraviolet curable resin.

[0068] Examples;! To 3, comparative examples;! To 5

Each component having the composition shown in Table 1 was charged into a reaction vessel equipped with a stirrer and stirred for 1 hour while controlling the liquid temperature at 50 ° C. to obtain a liquid curable resin composition.

[0069] Test Example 1

The liquid curable resin compositions obtained in the examples and comparative examples were cured by the following method to prepare test pieces, and the following evaluations were performed. The results are also shown in Table 1.

[0070] 1. Viscosity:

The viscosity at 25 ° C. of the compositions obtained in Examples and Comparative Examples was measured using a B-type viscometer.

[0071] 2. Young's modulus:

Apply a liquid curable resin composition on a glass plate using a 250 m thick applicator bar, and cure it by irradiating it with ultraviolet rays of lj / cm ² energy under nitrogen to form a film for measuring the yang ratio. Obtained. A strip-shaped sample was prepared from this film so that the stretched part had a width of 6 mm and a length of 25 mm, and a tensile test was performed at a temperature of 23 ° C. and a humidity of 50%. The tensile rate was lmm / min, and the tensile strength at 2.5% strain and Young's modulus were obtained.

[0072] 3. Breaking strength and breaking elongation:

Using a tensile tester (manufactured by Shimadzu Corporation, AGS-50G), the breaking strength and breaking elongation of the test piece were measured under the following measurement conditions.

Tensile speed: 50mm / min Distance between marked lines (measurement distance): 25mm

Measurement temperature: 23 ° C

Relative humidity: 50% RH

[0073] 4. Refractive index:

The resin composition was applied onto a glass plate using an applicator bar so that the film thickness was 200 m. 1. Oj / cm ² ultraviolet rays were irradiated under nitrogen to prepare a test piece. According to JIS K7105, the refractive index at 25 ° C. was measured using an Abbe refractometer manufactured by Atago Co., Ltd.

[0074] 5. Transparency (Haze):

The total light transmittance of the cured film was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). The measurement was performed on the cured film immediately after production and on the cured film after standing at 120 ° C. for 72 hours.

[0075] 6. Adhesion strength:

With respect to the compositions obtained in Examples and Comparative Examples, the adhesive strength stability of the cured products was measured. The liquid composition was applied onto a slide glass using an applicator with a thickness of 381 m, and irradiated with 0.1 lj / cm ² of ultraviolet light in a nitrogen atmosphere to obtain a cured film having a thickness of about 200 m. The cured film on the glass slide was allowed to stand for 24 hours at a temperature of 23 ° C and a humidity of 50%. Thereafter, a strip sample was prepared from the cured film so that the stretched portion had a width of 10 mm. This sample was subjected to an adhesion test using a tensile tester according to JIS Z0237. The adhesion force was determined from the tensile strength at a tensile speed of 50 mm / min.

[0076] 7. Curing rate:

Apply the composition onto a quartz glass plate using an applicator with a thickness of 200 m, and then use a 3.5 KW metal halide lamp (OMX, SMX-3500 / F—OS) in an air atmosphere! /, The cured film was obtained by irradiating ultraviolet rays under two conditions of 20 mj / cm ² and 1. Oj / cm ² . Next, after standing for 24 hours at 23 ° C and 50% relative humidity, a strip-shaped sample was prepared from this film so that the stretched part had a width of 6 mm and a length of 25 mm, and was used as a test piece. Next, the Young's modulus (MPa) of the test piece was measured with a tensile tester. Curing the value obtained by dividing the Young's modulus at 20 mj / cm ^{2 with the} ultraviolet ray by the Young's modulus at lj / cm ² It was speed.

[table 1]

Biscote 17F; 2 Perfluorooctyl cetyl (meth) acrylate (manufactured by Osaka Organic Chemical Co., Ltd.).

Irgacure 184; 1-hydroxycyclohexyl monophenolate ketone (Ciba Specialo Chemicals).

Lucirin; 2, 4, 6 Trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan).

Kyner ADS; copolymer of VDF / TFE / HFP vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene (manufactured by Arkema).

As is clear from Table 1, each example shows the composition viscosity, the cured product's Young's modulus' mechanical strength (breaking strength and elongation), refractive index, transparency (haze), and exposure to high temperature conditions. Even after being applied, good transparency is maintained. It also has good adhesion to quartz, which is the core layer material. On the other hand, in Comparative Example 1 in which the amount of the component (C) is excessive, the balance of the amount of the component (B) and the component (C) is lost, so the solubility of the component (A) is reduced. The cured product has poor transparency! In Comparative Example 2 using an ethylenically unsaturated group instead of component (A) and a hydroxyl group-containing fluorine-containing polymer, the viscosity of the composition is too low, and the fluorine polymer is contained in the composition. Since it does not dissolve, it has poor transparency. Further, in Comparative Example 3 using V, a fluoropolymer, which does not correspond to the component (A), the fluoropolymer does not dissolve in the composition, and therefore the transparency is poor.

Claims

Claims [1] The total amount of the composition is 100% by mass, and (A) the ethylenically unsaturated group-containing fluorine-containing copolymer is 20 to 65% by mass, and (B) the carbon number is 1; —Perfluoroalkyl ethyl (meth) acrylate is 20 to 60% by weight, CFF HHCIIII and RCFR RCIIII (C) Other than (A) and (B), aromatic structure and polar group A radiation-curable resin composition containing 10 to 35% by mass of a compound having 2 or more ethylenically unsaturated groups. [2] The component (A) is a structural unit (a) represented by the following formula (1), a structural unit (b) represented by the following formula (2), or a structural unit represented by the following formula (3) 2. The radiation curable resin composition according to claim 1, which is an ethylenically unsaturated group-containing fluorine-containing copolymer containing (c) and a structural unit (d) represented by the following formula (6). Structural unit (a):

[Chemical 1]

[Wherein R represents a fluorine atom, a fluoroalkyl group or a group represented by OR (R represents an alkyl group or a fluoroalkyl group)]

Structural unit (b):

[Chemical 2]

[Wherein, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, a group represented by one (CH 3) — OR ⁵ or OCOR ⁵ (R ⁵ represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group] Or a group represented by (5)

[Wherein R and R are the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]

[3] The radiation curable resin composition according to claim 1 or 2, further comprising (D) (meth) acrylic acid or a dimer thereof.

[4] The radiation-curable resin composition according to any one of claims 1 to 3, further comprising (E) a photopolymerization initiator.

[5] The radiation-curable resin composition according to any one of claims 1 to 4, which is used for forming an optical fiber clad layer.

[6] A cured film comprising a cured product of the radiation curable resin composition according to claim 1;

[7] A polymer-clad optical fiber having a core layer made of glass, quartz, or a transparent resin, and a clad layer made of a cured film according to claim 6, in contact with the outside of the core layer.