TWI664199B - Terminally modified soluble polyfunctional vinyl aromatic copolymer, method for producing the same, hardening composition, hardened material, film, hardenable composite material, laminate, metal foil with resin, varnish for circuit board material, hardening Resin composition, resin film for forming optical waveguide, and optical waveguide - Google Patents

Abstract

The present invention provides a soluble polyfunctional vinyl aromatic copolymer having improved heat resistance, thermal decomposition resistance, solvent solubility, processability, and compatibility with a specific resin, and a curable resin composition thereof. A terminally modified soluble polyfunctional vinyl aromatic copolymer in the presence of one or more catalysts (d) selected from the group consisting of a Lewis acid catalyst, an inorganic strong acid, and an organic sulfonic acid, A copolymer obtained by polymerizing a divinyl aromatic compound (a), a monovinyl aromatic compound (b), and a (meth) acrylate compound (c), and has a part of the end of the copolymer A terminal group derived from the (meth) acrylate compound (c).

Description

Terminal modified soluble polyfunctional vinyl aromatic copolymer Material, its manufacturing method, hardenable composition, hardened material, film, hardenable composite material, laminated body, metal foil with resin, varnish for circuit board material, hardenable resin composition, resin film for optical waveguide formation Optical waveguide

The present invention relates to a novel terminally modified soluble polyfunctional vinyl aromatic copolymer and a curable resin composition having improved heat resistance, compatibility and toughness. In particular, the present invention relates to a curable resin composition containing a novel terminally modified soluble polyfunctional vinyl aromatic copolymer, which is useful as a substrate material in the field of advanced electronic equipment in a field requiring high reliability, The present invention relates to a hardening composite material and a laminated body. The present invention relates to a resin composition for forming a light guide tube and a light guide tube which are excellent in transparency, light transmission loss, heat discoloration resistance, environmental reliability, and light transmission loss. Formation of a resin film and use of these optical waveguides.

With the increase in the amount of information communication in recent years, information communication in the high-frequency band is actively performed. In order to have more excellent electrical characteristics, in order to reduce the transmission loss in the high-frequency band, a method having a low dielectric constant and Low dielectric loss tangent, especially electrical insulation materials with small change in dielectric properties after absorbing water. Furthermore, printed circuit boards or electronic components using these electrical insulating materials are exposed to high-temperature reflow soldering during mounting. Therefore, it is desirable to have a high heat resistance, that is, a material that exhibits a high glass transition temperature. material. In particular, lead-free solders having a high melting point have recently been used due to environmental problems, and therefore, electrical insulation materials having higher heat resistance have been required. In response to these requirements, hardened resins using vinyl-based compounds having various chemical structures have previously been proposed.

As such a hardening resin, for example, Patent Document 1 discloses a soluble polyfunctional vinyl aromatic copolymer, which divinates aromatics in the presence of a Lewis acid catalyst and a specific structured initiator. A family compound and a monovinyl aromatic compound are obtained by polymerization in an organic solvent at a temperature of 20 ° C to 100 ° C. In addition, Patent Document 2 discloses a method for producing a soluble polyfunctional vinyl aromatic copolymer, which uses a Lewis acid catalyst and a specific structure initiator in the presence of a quaternary ammonium salt. A soluble polyfunctional vinyl aromatic compound having a controlled molecular weight distribution by subjecting a singular amount of a divinyl aromatic compound at 20 mol% to 100 mol% to cationic polymerization at a temperature of 20 ° C to 120 ° C. Group co-polymer manufacturing method. The soluble polyfunctional vinyl aromatic copolymer obtained by the techniques disclosed in the two patent documents is excellent in solvent solubility and processability. By using the soluble polyfunctional vinyl aromatic copolymer, it is possible to obtain A hardened product having a high glass transition temperature and excellent heat resistance.

Since the soluble polyfunctional vinyl aromatic copolymer obtained by these techniques has a polymerizable double bond, it can provide a hardened product having a high glass transition temperature by hardening it. Therefore, it can be said that this hardened | cured material or soluble polyfunctional vinyl aromatic copolymer is a polymer excellent in heat resistance or its precursor. In addition, the soluble polyfunctional vinyl aromatic copolymer is copolymerized with other radical polymerizable monomers to provide a cured product. The cured product is also excellent in heat resistance. Polymer.

However, from the standpoint of compatibility between the soluble polyfunctional vinyl aromatic copolymers disclosed in Patent Documents 1 and 2 and other curable resins, or heat discoloration resistance after curing, the polarities are high. The compatibility or solubility between the epoxy compounds or phenol resins is insufficient, and the thermal decomposition resistance at high process temperatures is also insufficient. Therefore, it is often the case that an opaque composition is provided depending on the type of the epoxy compound or the phenol resin, and it is difficult to produce a uniform cured product of the epoxy compound or the phenol resin and the soluble polyfunctional vinyl aromatic copolymer. In addition to the disadvantages of a small degree of freedom in formulating the formulation and a low toughness of the hardened material, there may be defects such as swelling or peeling due to a high thermal history near 280 ° C to 300 ° C.

In addition, Patent Document 3 discloses a soluble polyfunctional vinyl aromatic copolymer which is a copolymer obtained by copolymerizing a divinyl aromatic compound (a) and a monovinyl aromatic compound (b). A polymer has a chain hydrocarbon group or an aromatic hydrocarbon group via an ether bond or a thioether bond at a part of its terminal group.

However, the soluble polyfunctional vinyl aromatic copolymer has insufficient toughness. Therefore, sufficient mechanical properties cannot be obtained in the hardened material of the hardenable composition. Therefore, there is insufficient interlayer peel strength in the hardened material of the composite. Issues such as reduced reliability. In addition, although it is described that an ester compound can be used as an accelerator, specific examples of the usable ester compound include ethyl acetate, methyl propionate, and the like, which do not have introduction into a terminal of a soluble polyfunctional vinyl aromatic copolymer. A functional ester compound with a functional group. Therefore, the terminal group of the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 3 contains a chain hydrocarbon compound derived from an alcoholic hydroxyl group and an aromatic group. An aromatic hydrocarbon compound, a chain hydrocarbon compound having a thiol thiol group, and a chain hydrocarbon group or an aromatic hydrocarbon group having an ether bond or a thioether bond via an ether bond or a thioether bond are used as terminal groups.

On the other hand, Patent Documents 4 and 5 disclose a polyfunctional vinyl aromatic copolymer having a terminal group derived from an aromatic ether compound and a thio (meth) acrylate derived A soluble multifunctional vinyl aromatic copolymer of a terminal group of a compound. However, although the soluble polyfunctional vinyl aromatic copolymers disclosed in these patent documents have improved toughness, they have the following problems: they do not have low mediators in the high-frequency band accompanying the increase in information traffic in recent years. Electrical properties cannot be applied to cutting-edge technical fields that require high functionality and high electrical, thermal, and mechanical properties, such as the cutting-edge electrical and electronic fields. In addition, after the wet heat history, the adhesiveness at the interface between the soluble polyfunctional vinyl aromatic copolymer and the glass cloth is reduced, and therefore there is a disadvantage that it cannot be used as a substrate material in a field requiring high reliability.

On the other hand, Patent Document 6 discloses a curable resin composition including a polyphenylene ether oligomer having vinyl groups at both ends, and having a divinyl-containing aromatic compound and an ethyl vinyl group. A polyfunctional vinyl aromatic copolymer of a singular unit of an aromatic compound. However, the curable resin composition using a soluble polyfunctional vinyl aromatic copolymer has insufficient interlayer peeling strength, plating peeling strength, and dielectric properties after a wet heat history, so it cannot be used as a substrate in the field of advanced electronic equipment. Material disadvantage.

Patent Document 7 discloses a curable resin composition including A polyfunctional vinyl aromatic copolymer having a structural unit derived from a single body containing a divinyl aromatic compound and an ethylvinyl aromatic compound, and containing a polyfunctional aromatic vinyl copolymer selected from the group consisting of an epoxy group, a cyanate group, and ethylene. A thermosetting resin having one or more functional groups selected from the group consisting of an alkyl group, an ethynyl group, an isocyanate group, and a hydroxyl group. However, this curable resin composition using a soluble polyfunctional vinyl aromatic copolymer has insufficient plating properties, and therefore has a problem that it cannot be applied to a high-tech state-of-the-art technical field that requires a high degree of miniaturization.

However, in the high-speed and high-density signal transmission between electronic components or wiring boards, in the previous transmission using electrical wiring, mutual interference or attenuation of signals became an obstacle, and the limits of high-speed and high-density began to be seen. In order to break this limit, development of a so-called optical interconnection technology using an optical connection between electronic components or between wiring boards is being performed. As an optical transmission tube, a polymer optical waveguide has attracted attention from the viewpoints of ease of processing, low cost, high degree of freedom in wiring, and high density.

As the form of the polymer optical waveguide, it is generally considered suitable to be a rigid optical waveguide fabricated on a hard supporting substrate such as glass epoxy resin which is intended for the application of a photoelectric hybrid substrate, or a substrate which does not have a rigid connection where the substrates are connected. A flexible light waveguide supporting a substrate.

Furthermore, by using a photoelectric composite flexible wiring board in which a flexible wiring board and a light waveguide are integrated and integrated, the degree of freedom of installation can be further improved.

From the standpoint of the environment in which the machine is used, the mounting of parts, etc., the polymer optical waveguide requires transparency (low light propagation loss), and also For heat resistance and environmental reliability. In addition, from the viewpoint of the strength and handleability of the optical waveguide, the demand for toughness is also increasing. Furthermore, as for the manufacturing process of the light guide tube, a method for easily forming a core pattern is required. As one of the methods, a pattern forming method using exposure development widely used in a manufacturing process of a printed wiring board can be cited. As such a material, a light waveguide material containing a (meth) acrylic polymer is known (for example, refer to Patent Documents 8 to 11).

The optical waveguide materials described in Patent Documents 8 and 9 can form a core pattern by exposure and development, have transparency at a wavelength of 850 nm, and have good light transmission loss after a high-temperature and high-humidity storage test, but there is no heat resistance. Evaluation of performance, for example, no specific description of test results such as light propagation loss after reflow soldering test.

In addition, the optical waveguide material described in Patent Document 10 exhibits excellent optical transmission loss and good heat resistance, but is fragile and cannot satisfy strong toughness.

In addition, the optical waveguide material described in Patent Document 11 has transparency at a wavelength of 850 nm and is excellent in toughness, but there is no evaluation of heat resistance, such as specific results of test results such as light propagation loss after a reflow test. There is no description of environmental reliability, for example, there is no specific description of test results such as light propagation loss after a high-temperature and high-humidity storage test or a temperature cycle test.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-123873

[Patent Document 2] Japanese Patent Laid-Open No. 2005-213443

[Patent Document 3] Japanese Patent Laid-Open No. 2007-332273

[Patent Document 4] Japanese Patent Laid-Open No. 2010-229263

[Patent Document 5] Japanese Patent Laid-Open No. 2010-209279

[Patent Document 6] WO2005 / 73264

[Patent Document 7] Japanese Patent Laid-Open No. 2006-274169

[Patent Document 8] Japanese Patent Laid-Open No. 2006-146162

[Patent Document 9] Japanese Patent Laid-Open No. 2008-33239

[Patent Document 10] Japanese Patent Laid-Open No. 2006-71880

[Patent Document 11] Japanese Patent Laid-Open No. 2007-122023

In view of such background technology, an object of the present invention is to provide a novel terminally modified soluble polyfunctional vinyl aromatic copolymer with improved heat resistance, compatibility, and toughness, and to provide a cutting-edge that requires high reliability A hardenable resin composition useful as a substrate material in the field of electronic equipment, a hardenable composite material and a laminate thereof, and a hardenable resin composition excellent in transparency, low light transmission loss, heat resistance, environmental reliability, and toughness Materials, in particular, a curable resin composition for a light waveguide, a resin film for forming a light waveguide, and a light waveguide using the same, which form a light waveguide with good productivity and workability.

As a result of intensive research, the present inventors have found that one or more kinds of ethylene containing a specific terminally modified soluble polyfunctional vinyl aromatic copolymer, having one or more unsaturated groups and having specific terminal groups The curable resin composition of the base compound and the radical polymerization initiator can solve the above problems, and completed the present invention.

That is, the present invention is a terminally modified soluble polyfunctional vinyl aromatic copolymer comprising a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit, and (2) and a copolymer of a terminal group represented by the following formula (3), which is characterized by being solvent-soluble and polymerizable.

(Here, R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms or hydrogen, R ² to R ³ represent a hydrocarbon group having 1 to 18 carbon atoms, and R ⁴ represents hydrogen or methyl group)

It is preferable that the said copolymer is a unit which the divinyl aromatic compound (a) contains the structural unit which does not have a vinyl group, and the structural unit which has one vinyl group.

The copolymer preferably has a number average molecular weight Mn of 300 to 100,000 and a molecular weight distribution (Mw / Mn) of 100.0 or less.

The copolymer is preferably an introduction amount (c1) of a terminal group represented by the formula (3) and satisfies the following formula (4) (c1) ≧ 1.0 (units / molecule) (4). The Mohr fraction (a) of the structural unit derived from a divinyl aromatic compound and the Mohr fraction (b) of a structural unit derived from a monovinyl aromatic compound in the following formula (5) 0.05 ≦ (a) / {(a) + (b)} ≦ 0.95 (5), and the Mohr fraction (c) of the terminal group represented by the formulas (2) and (3) satisfies the following formula (6) ) 0.005 ≦ (c) / {(a) + (b)} <2.0 (6), and it is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.

In addition, the present invention is a method for producing a terminally modified soluble polyfunctional vinyl aromatic copolymer, which is used for producing the terminally modified soluble polyfunctional vinyl aromatic copolymer, and is characterized in that it is selected from a Lewis acid In the presence of one or more catalysts (d) in the group consisting of a catalyst, an inorganic strong acid, and an organic sulfonic acid, the divinyl aromatic compound (a) and the monovinyl aromatic compound (b), Polymerization with the (meth) acrylate compound (c) represented by the following formula (1).

(Here, R ¹ to R ^{4 have} the same meaning as in formulas (2) and (3))

In the method for producing the copolymer, it is preferable to use a divinyl aromatic compound (100 mol% with respect to a total of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b). a) 5 mol% to 95 mol%, monovinyl aromatic compound (b) 95 mol% to 5 mol%, and further to 100 mol of all the single bodies, use the formula (1) The (meth) acrylate compound (c) shown is 0.5 to 500 moles, and the catalyst (d) is 0.001 to 10 moles relative to the (meth) acrylate compound (c) 1 mole. Mol, and polymerize these polymerization raw materials in a uniform solvent having a dielectric constant of 2.0 to 15.0.

Furthermore, the present invention is a hardenable composition, comprising the terminal modified soluble polyfunctional vinyl aromatic copolymer and a radical polymerization initiator.

The curable composition may contain modified polyphenylene ether (XC).

The curable composition may contain two or more selected from one molecule Epoxy resin with an aromatic structure, epoxy resin having two or more epoxy groups and a cyanurate structure in one molecule, and / or epoxy resin having two or more epoxy groups in one molecule, and One or more epoxy resins (XD) and a hardener (XE) in the group consisting of alicyclic epoxy resins.

Furthermore, this invention is a hardened | cured material obtained by hardening | curing the said hardenable composition, or the film which formed the said hardenable composition into a film form.

Furthermore, the present invention is a hardenable composite material, which includes the hardenable composition and a base material, and is characterized in that the base material is contained in a ratio of 5 wt% (weight percent) to 90 wt%, and the present invention is a hardening A hard composite material is obtained by hardening the hardenable composite material, and the present invention is a laminated body characterized by comprising a layer of the hardened composite material and a metal foil layer.

In addition, the present invention is a metal foil with a resin, characterized in that a film made of the curable composition is provided on one side of the metal foil, or the present invention is a varnish for a circuit board material, The curable composition is dissolved in an organic solvent.

In addition, the present invention is also a terminally modified soluble polyfunctional vinyl aromatic copolymer, which is one or more catalysts selected from the group consisting of a Lewis acid catalyst, an inorganic strong acid, and an organic sulfonic acid ( The copolymer obtained by reacting a divinyl aromatic compound (a), a monovinyl aromatic compound (b), and a (meth) acrylate compound (c) in the presence of d) is characterized in that : A part of the end of the copolymer has a (meth) acrylate-based compound (c) derived from the formula (2) and the formula (3), and the number is averaged. The molecular weight Mn is 300 to 100,000, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is 100.0 or less, and the introduction amount (c1) of the terminal group satisfies the following formula (3) ) (c1) ≧ 1.0 (units / molecule) (3), Mohr fraction (A) of the structural unit derived from the divinyl aromatic compound in the copolymer and the structure derived from the monovinyl aromatic compound The Mohr fraction (B) of the unit satisfies the following formula (4) 0.05 ≦ (A) / {(A) + (B)} ≦ 0.95 (4), and the Mohr fraction (C) of the terminal group satisfies The following formula (5) 0.005 ≦ (C) / {(A) + (B)} <2.0 (5) is soluble in toluene, xylene, tetrahydrofuran, dichloroethane, or chloroform.

In addition, the present invention is also a method for producing a terminally modified soluble polyfunctional vinyl aromatic copolymer, which comprises a divinyl aromatic compound (a), a monovinyl aromatic compound (b), and (methyl) ) A method for producing a copolymer by reacting an acrylate compound (c), which is characterized by 100 mol% with respect to a total of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b), Dimolecular aromatic compound (a) 5 mol% to 95 mol%, monovinyl aromatic compound (b) 95 mol% to 5 mol%, and then 100 mol relative to all single bodies, Using a (meth) acrylate compound (c) represented by the formula (1) from 0.5 mol to 500 mol, and selected from the group consisting of a Lewis acid catalyst, an inorganic strong acid, and an organic sulfonic acid One or more of the catalysts (d) are obtained by polymerizing at a temperature of 20 ° C to 120 ° C in a homogeneous solvent obtained by dissolving these polymerization raw materials in a solvent having a dielectric constant of 2.0 to 15.0. The end of the copolymer has a terminal group derived from the (meth) acrylate compound (c) represented by the formula (2) to formula (3) of 1.0 (units / molecule) or more, and is soluble in Copolymers in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.

Furthermore, the present invention is a curable resin composition, which comprises the component (A): having a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit; and (2) and a copolymer of a terminal group represented by the formula (3), and having polymerizable and solvent-soluble terminally modified soluble polyfunctional vinyl aromatic copolymer; (B) component: 1 in the molecule One or more vinyl compounds having more than one unsaturated group; and (C) a component: a radical polymerization initiator; and (A) a compounded amount of 5 to 94.9 wt%, and (B) a compounded amount It is 5.0 wt% to 85 wt%, and the blending amount of the component (C) is 0.1 wt% to 10 wt%.

(A) The component is preferably a polymerizable solvent-soluble terminally modified soluble polyfunctional vinyl aromatic copolymer, which is a divinyl A copolymer of an aromatic compound (a) unit and a monovinyl aromatic compound (b) unit, and a terminal group represented by the formula (2) and the formula (3); and the divinyl group The aromatic compound (a) unit has a structural unit represented by the following formula (a1), a structural unit represented by the following formula (a2), and a structural unit represented by the following formula (a3). The monovinyl aromatic compound (b) unit has a structural unit represented by the following formula (b).

It is preferable to make the divinyl aromatic compound (a) and monoethylene in the presence of one or more catalysts (d) selected from the group consisting of a Lewis acid catalyst, an inorganic strong acid, and an organic sulfonic acid. The copolymer obtained by polymerizing the base aromatic compound (b) and the (meth) acrylate compound (c) represented by the formula (1), may be performed using other raw materials or conditions. The obtained copolymer was polymerized.

(Here, R ¹⁵ , R ¹⁶ and R ¹⁷ represent an aromatic hydrocarbon group having 6 to 30 carbon atoms)

(Here, R ¹⁸ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. Z represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydrogen atom)

In addition, the present invention is a curable resin composition for forming an optical waveguide, which is characterized in that the curable resin composition is used for forming an optical waveguide.

In the curable resin composition for forming an optical waveguide, it is preferable that the component (C) contains a photoradical polymerization initiator. The component (B) includes a vinyl compound having a structural unit represented by the following general formula (16) or (17), or a curable vinyl polymer produced from the vinyl compound. should.

[Chemical 5]

(In the formula, R ⁵ and R ⁸ represent a hydrogen atom or a methyl group, and X ¹ and X ² represent a group consisting of a single bond, or an ester bond, an ether bond, a thioester bond, a thioether bond, and a amide bond. (One or more bonds in the group are divalent organic groups having 1 to 20 carbon atoms, and R ⁶ and R ⁹ represent hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms)

The present invention is a resin film for forming a light waveguide, which is formed using the curable resin composition for forming the light waveguide. Furthermore, the present invention is an optical waveguide including a curable resin set for forming the optical waveguide. The product or the core portion and / or the cladding layer formed by the resin film for forming a light waveguide. The optical waveguide preferably has a light propagation loss of 0.3 dB / cm or less in a light source with a wavelength of 850 nm.

The heat-resistance, compatibility, and toughness of the hardened | cured material obtained from the terminal modification of the soluble polyfunctional vinyl aromatic copolymer or the material containing the same are improved. Moreover, according to the manufacturing method of this invention, the said copolymer can be manufactured efficiently. In addition, by using the terminally modified soluble polyfunctional vinyl aromatic copolymer of the present invention as a hardening compound, the molecule has a free volume with a large molecular size in the molecule and few polar groups, so that a high degree of low intermediation can be obtained. Electrically hardened product, and can simultaneously achieve good adhesion, plating properties and dielectric loss tangent characteristics after wet heat history.

Furthermore, the curable resin composition of the present invention is excellent in transparency, heat resistance, and toughness, and can form a high-precision thick film. It is useful not only as a curable resin composition in a transparent material, but also for forming a light guide It is useful for forming a resin composition or a resin film for forming a highly productive optical waveguide. In addition, by using such a resin composition or a resin film for forming a light waveguide, a light waveguide having excellent transparency, heat resistance, environmental reliability, and toughness can be manufactured.

1‧‧‧ light-guided tube

2‧‧‧ core

3‧‧‧ upper cladding

4‧‧‧ lower cladding

5‧‧‧ substrate (protective film)

1 (a) to 1 (d) are cross-sectional views illustrating the configuration of a light waveguide.

FIG. 2 is a diagram showing a temperature distribution in a reflow furnace in a reflow test.

The soluble polyfunctional vinyl aromatic interpolymer of the present invention is a polymerizable solvent-soluble terminally modified soluble polyfunctional vinyl aromatic copolymer, which includes a structural unit having no vinyl group and a polymer having one vinyl group. A divinyl aromatic compound (a) unit, a monovinyl aromatic compound (b) unit, and a terminal group represented by the formula (2) and the formula (3).

The terminal modified soluble polyfunctional vinyl aromatic copolymer may be in the presence of one or more catalysts (d) selected from the group consisting of a Lewis acid catalyst, an inorganic strong acid, and an organic sulfonic acid. A copolymer obtained by polymerizing a divinyl aromatic compound (a) and a monovinyl aromatic compound (b) and a (meth) acrylate compound (c) represented by the formula (1).

In the formula, R ¹ represents a hydrocarbon group having 1 to 18 carbons or hydrogen, R ² to R ³ represent a hydrocarbon group having 1 to 18 carbons, and R ⁴ represents hydrogen or methyl. Preferred R ¹ to R ³ are alkyl groups having 1 to 6 carbons such as methyl and ethyl.

In the soluble polyfunctional vinyl aromatic copolymer of the present invention, a divinyl aromatic compound (a), a monovinyl aromatic compound (b), and (meth) acrylic acid are prepared in the presence of a catalyst (d). A copolymer obtained by polymerizing the ester compound (c) is preferable, and at least a part of the terminal thereof is modified by a terminal group derived from the (meth) acrylate compound (c).

This copolymer has a structural unit derived from a divinyl aromatic compound (a) and a structural unit derived from a monovinyl aromatic compound (b). Molar fraction (a) of a structural unit derived from a divinyl aromatic compound in a copolymer and molar fraction (b) of a structural unit derived from a monovinyl aromatic compound to satisfy (a) /{(a)+(b)}=0.05~0.95 is appropriate. It is preferably 0.2 to 0.8, and more preferably 0.3 to 0.7. If it is less than 0.05, heat resistance is reduced, and therefore there is a possibility that a good shape of the light guide tube cannot be maintained due to a thermal history in the process of forming the light guide tube and the formation of electrical wiring. If it is larger than 0.95, the molecular weight of the copolymer is likely to increase, and the etching characteristics may be deteriorated due to an excessively high crosslinking density, and it may be difficult to form an optical waveguide having an excellent shape and a small optical loss.

The structural unit derived from the divinyl aromatic compound (a) includes a structural unit having no vinyl group and a structural unit having one vinyl group. It is considered that it is preferable to have the structural unit represented by said Formula (a1), Formula (a2), and Formula (a3). Hereinafter, these structural units are referred to as units (a1) to (a3).

The structural unit having one vinyl group, such as the unit (a1) and the unit (a3), imparts polymerizability to the copolymer, and the copolymer is made multifunctional as a curable resin. The unit (a2), which is a structural unit without a vinyl group, imparts a crosslinked structure and increases the degree of branching. However, if the crosslinking proceeds excessively, it will harden and become solvent-insoluble. Therefore, there must be units (a1) and units that do not participate in crosslinking (a3).

In addition, the total molar fraction (a) of the structural unit derived from the divinyl aromatic compound and the molar fraction (b) of the structural unit derived from the monovinyl aromatic compound are added to the copolymer. The content of the unit (a1) and the unit (a3) is preferably 10 mol% to 60 mol%, preferably 15 mol% to 50 mol%, and more preferably 20 mol% to 40 mol%. . The content of the unit (a2) is preferably 5 mol% to 50 mol%, and more preferably 10 mol% to 40 mol%. The molar ratio of the unit (a1) to the unit (a3) is preferably in the range of 99.999: 0.001 to 1:99. Units in the copolymer (a1) Compared with the unit (a3), since the polymerizability at the time of hardening is good, the range of 99.99: 0.01-30: 70 is preferable. A more preferable range is 99.99: 0.01 to 50:50.

From another viewpoint, the content of the structural unit having one vinyl group in the structural unit derived from the divinyl aromatic compound is preferably 10 mol% to 90 mol%, and more preferably 20 mol% to 80 mol%, more preferably 30 mol% to 70 mol%. However, the content of the structural unit or the degree of polymerization is controlled so as to show solvent solubility.

In the formulas (a1), (a2), and (a3), R ¹⁵ , R ¹⁶ , and R ¹⁷ represent aromatic hydrocarbon groups having 6 to 30 carbon atoms, but these are derived from divinyl aromatic compounds. So understand from its description. In formula (b), R ¹⁸ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, and Z represents an alkyl group having 1 to 6 carbon atoms, and an alkoxy group or hydrogen atom having 1 to 6 carbon atoms. Since it is a monovinyl aromatic compound, it is understood from the description.

The content of the structural unit derived from the divinyl aromatic compound (a) in the copolymer is preferably 5 mol% to 95 mol%, preferably 10 to 90 mol%, and more preferably 20 to 70. Mohr%.

If the content is small, the heat resistance decreases with the decrease in cross-linking density. Therefore, it is difficult to maintain a good shape when subjected to a thermal history in the optical waveguide formation process and the like. An optical waveguide tube having an excellent structure.

In other perspectives, 100 mol relative to the total of all structural units %, Preferably 30 mol% to 90 mol% containing the structural unit (a). The structural unit (a) contains a vinyl group as a crosslinking component for expressing heat resistance. On the other hand, the structural unit (b) derived from a monovinyl aromatic compound does not have the vinyl group, and therefore imparts moldability. Wait.

In addition to the structural unit derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b), the copolymer of the present invention has a (meth) acrylate compound (c) derived from The terminal group represented by Formula (2) and Formula (3) is a structural unit. When the molar ratio of each structural unit is (a), (b), (c), the molar fraction (c) / {(a) + (b)} of the terminal group is 0.005 or more. At least 2.0, preferably 0.01 to 1.5, and more preferably 0.05 to 1.0.

By introducing the terminal group to the end of the copolymer in such a way as to satisfy the relationship, it can be made to have low light loss, high toughness, excellent heat resistance, and compatibility with (meth) acrylate compounds A resin composition or product that is excellent in molding processability. When the Mohr fraction of the terminal group is small, the compatibility with the (meth) acrylate compound and the moldability are decreased. When the Mohr fraction of the terminal group is large, the dimensional change after the wet heat history is large. The characteristics are degraded.

In each molecule of the soluble polyfunctional vinyl aromatic copolymer, the introduction amount (c1) of the terminal group represented by the formula (3) is on average 1.0 or more, and preferably 2 to 5.

The Mn of the soluble polyfunctional vinyl aromatic copolymer (here, Mn is a standard polystyrene-equivalent number average molecular weight measured by gel permeation chromatography) is preferably 300 to 100,000, and preferably 400 to 50,000, more preferably 500 ~ 10,000. If Mn is too low, the amount of monofunctional copolymers contained in the copolymer will increase. Therefore, the heat resistance of the cured product tends to decrease. If it is too high, gelation tends to occur, viscosity increases, and molding tends to occur. The processability tends to decrease. The value of the molecular weight distribution (Mw / Mn) is preferably 100.0 or less, more preferably 50.0 or less, and even more preferably 1.5 to 10.0. The best is 1.5 ~ 5.0. When the value of the molecular weight distribution (Mw / Mn) is too high, there is a tendency that the processing characteristics of the copolymer are lowered and gelation is liable to occur.

The soluble polyfunctional vinyl aromatic copolymer is soluble in a solvent selected from toluene, xylene, tetrahydrofuran, dichloroethane, or chloroform, and is advantageously soluble in any of the solvents. Here, the term "soluble in a solvent" means that 5 g or more is dissolved in 100 g of a solvent at 25 ° C, and preferably 10 g or more is dissolved. Since it is a polyfunctional copolymer that is soluble in a solvent, a part of the vinyl group of the divinyl aromatic compound remains without being crosslinked, and it must be polymerized so as to have a moderate degree of crosslinking. The polymerization method will be described later.

The soluble polyfunctional vinyl aromatic copolymer has a terminal modified from the terminal group, and therefore has high compatibility with a (meth) acrylate-based compound. Therefore, when the curable resin composition containing a (meth) acrylate-based compound is cured, it becomes one having excellent uniform curing properties or transparency.

Next, a method for producing a terminally modified soluble polyfunctional vinyl aromatic copolymer will be described.

This copolymer uses a catalyst (d) such as a Lewis acid catalyst to combine a divinyl aromatic compound (a) and a monovinyl aromatic compound (b) with (A) represented by the formula (1). Group) is produced by polymerizing an acrylate compound (c). usually, The (meth) acrylate compound has no cationic polymerizability, and therefore does not copolymerize with a vinyl aromatic compound. However, when the (meth) acrylate compound becomes an ester with a secondary alcohol or a tertiary alcohol, in the presence of an acid catalyst such as a Lewis acid catalyst, it cracks at the secondary or tertiary carbon, and is cleaved with the secondary or tertiary carbon. The first or third carbocation produces a (meth) acrylate anion. Polymerization then begins with the secondary or tertiary carbocation. However, it is inferred that the efficiency of the starter of the initiation reaction is not necessarily high, and a part thereof becomes an alkane such as butane and is discharged to the outside of the system. In addition, the (meth) acrylic acid anion generated by the initial reaction is reacted with a carbocation at the end of the active species and rebonded to introduce a (meth) acrylic acid unit to the end of the stop.

As described above, as the terminal group derived from the (meth) acrylate compound (c), there are the terminal groups represented by the formula (2) and the formula (3), and the terminal groups represented by the formula (2) Contains a secondary alkyl group or a tertiary alkyl group, but a part of them is converted into an alkane concurrently and discharged to the outside of the system. Therefore, it can be considered that the amount of the terminal group of the formula (2) becomes a terminal group (c1) of the formula (3). The amount is slightly less. Therefore, it can be said that the amount of the terminal group is preferably specified by the amount of the terminal group (c1).

The amount of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b) is 100 mol% with respect to the total of the two, and the divinyl aromatic compound (a) is 5 mol% to 95 mol%. Ear mole%, preferably 95 mole% to 5 mole% of the monovinyl aromatic compound (b), more preferably 15 mole% to 70 mole% of the divinyl aromatic compound (a), monovinyl aromatic Group compound (b): 85 mol% to 30 mol%.

Divinyl aromatic compound (a) Branches the copolymer It is polyfunctional and plays an important role as a cross-linking component for expressing heat resistance when the copolymer is thermally hardened. As examples of the divinyl aromatic compound (a), divinylbenzene (including each isomer), divinylnaphthalene (including each isomer), and divinylbiphenyl (containing each Isomers), but is not limited to these compounds. These compounds may be used alone or in combination of two or more. From the viewpoint of moldability and heat discoloration resistance, divinylbenzene (interstitial, counter, or a mixture of these isomers) is more preferred.

The monovinyl aromatic compound (b) improves the solvent solubility and processability of the copolymer. Examples of the monovinyl aromatic compound (b) include styrene, a nucleoalkyl-substituted monovinyl aromatic compound, an α-alkyl-substituted monovinyl aromatic compound, a β-alkyl-substituted styrene, and an alkoxy group. But not limited to these compounds. In order to prevent the gelation of the copolymer, to improve the solubility and processing properties of the solvent, and from the viewpoint of cost and ease of availability, styrene and ethyl vinylbenzene (including each isomer) can be particularly preferably used. ), Ethyl vinyl biphenyl (including each isomer). From the viewpoint of dielectric properties, ethyl vinylbenzene (intermediate, counter, or a mixture of these isomers) is more preferred.

In addition, when producing a copolymer, in addition to the divinyl aromatic compound (a) and the monovinyl aromatic compound (b), a trivinyl aromatic compound, Other units (e) such as a trivinyl aliphatic compound, a divinyl aliphatic compound, and a monovinyl aliphatic compound are introduced into the copolymer.

Specific examples of the other singular body (e) include 1,3,5-trivinyl Benzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diacrylate, butadiene, and the like are not limited to these compounds. These compounds can be used alone or in combination of two or more. It is suitable to use the other singular body (e) in the range of less than 30 mol% of all the singular bodies. Thereby, with respect to the total amount of the structural unit in a copolymer, the structural unit derived from the other single body component (e) is made into the range of less than 30 mol%. In addition, when referring to all singly bodies, (meth) acrylic acid is included in addition to singly bodies having a polymerizable double bond, such as a divinyl aromatic compound (a) and a monovinyl aromatic compound (b). Ester-based compound (c).

The (meth) acrylate-based compound (c) is represented by the formula (1), and a cracking reaction occurs with the catalyst (d) during the initial reaction to generate a secondary or tertiary carbon cation. Polymerize the active species, and re-bond the (meth) acrylic anion anion produced by the initiation reaction with a carbocation at the end of the polymerizable species as a chain transfer agent, thereby enabling the The end provides functions such as toughness, low light transmission loss, and processability.

The terminal group generated from the (meth) acrylate-based compound (c) is represented by the formula (2) and the formula (3), and it is considered that the terminal group and the stop terminal of the copolymer are each bonded.

As described above, the (meth) acrylic acid ester-based compound (c) is one kind of a single substance, but it is also a polymerization additive. In a copolymer, the end group (one of the structural units) is imparted to the terminal group by a chain transfer reaction, and thus it is also a chain transfer agent.

As the (meth) acrylate compound (c), methacrylic acid can be preferably used from the viewpoints of reactivity, ease of availability, and heat resistance of a cured product. Third butyl ester, second butyl methacrylate, third butyl acrylate, or second butyl acrylate. From the viewpoint of the reaction rate, the third butyl methacrylate or the third butyl acrylate can be more preferably used.

The used amount of the (meth) acrylate compound (c) is 0.5 mol to 300 mol based on 100 mol of the total of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b). Preferably, it is preferably 1 to 200 mol, and more preferably 10 to 150 mol. If it is used in too small an amount, not only the amount of the terminal groups introduced will decrease and functions such as toughness will decrease, but the molecular weight and molecular weight distribution will increase, and the moldability will deteriorate. In addition, if it is used in an excessively large amount, in addition to a significant decrease in the polymerization rate and a decrease in productivity, the refractive index decreases. At the time of the polymerization reaction, the (meth) acrylate compound (c) reacts with the catalyst (d) to start the polymerization reaction and stop growing after the terminal group is formed. The used amount and reaction conditions are selected so that the introduction amount of the terminal group derived from the (meth) acrylate-based compound (c) becomes the range set in the description of the copolymer.

In the polymerization reaction, a divinyl aromatic compound (a), a monovinyl aromatic compound (b), a (meth) acrylate compound (c), and a catalyst (d) are used. In a homogeneous solvent prepared by dissolving in a solvent having a dielectric constant of 2.0 to 15.0, it is preferable to perform cationic copolymerization at a temperature of 20 ° C to 120 ° C to obtain a terminally modified copolymer.

As the catalyst (d), one or more members selected from the group consisting of a Lewis acid catalyst, an inorganic strong acid, and an organic sulfonic acid are used.

As a Lewis acid catalyst, as long as it contains metal ions (acids) and coordination Compounds (bases) that can accept electron pairs can be used without particular restrictions. Among the Lewis acid catalysts, from the viewpoint of the thermal decomposition resistance of the obtained copolymer, particularly preferred are B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Ti, W, Divalent to hexavalent metal fluorides such as Zn, Fe, and V. Examples of the strong inorganic acid include sulfuric acid, hydrochloric acid, and phosphoric acid. Specific examples of the organic sulfonic acid include benzenesulfonic acid and p-toluenesulfonic acid. These catalysts can be used alone or in combination of two or more. From the viewpoint of controlling the molecular weight and molecular weight distribution of the obtained copolymer and the polymerization activity, an ether (diethyl ether, dimethyl ether, etc.) complex of boron trifluoride can be preferably used.

The catalyst (d) is preferably used in the range of 0.001 mol to 10 mol relative to 1 mol of the (meth) acrylate-based compound (c), and more preferably 0.001 mol to 1 mol. If it exceeds 10 mol, the polymerization rate becomes too high, and therefore it is not only difficult to control the molecular weight distribution, but also the amount of introduction of terminal groups derived from the compound (c) is reduced.

When producing a terminally modified soluble polyfunctional vinyl aromatic copolymer, a primary alcohol selected from ethyl acetate, n-propyl acetate, and n-butyl acetate, and a carboxylic acid ((methyl)) As the accelerator (f), one or more of the ester compounds obtained from acrylic acid) or dialkyl ketones having 1 to 30 carbon atoms such as methyl ethyl ketone and methyl isobutyl ketone are used. The use amount of the accelerator (f) is less than 300 mol, and preferably less than 200 mol, with respect to the total of 100 mol of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b). , More preferably less than 150 mol. During the polymerization reaction, the accelerator interacts with the active species or the catalyst (d), which is effective for improving the selectivity of the reaction and controlling the molecular weight. However, if it is used excessively, The polymerization rate decreased significantly and the yield of the copolymer decreased.

This polymerization reaction is preferably performed in one or more organic solvents having a dielectric constant of 2 to 15 as a solvent of the terminally modified soluble polyfunctional vinyl aromatic copolymer produced by dissolution. As an organic solvent, as long as it is a compound that does not substantially hinder cationic polymerization, and dissolves catalysts, polymerization additives, accelerators, monomers, and polyfunctional vinyl aromatic copolymers to form a uniform solution, the dielectric constant is 2 In the range of ~ 15, there is no particular limitation, and it can be used alone or in combination of two or more. When the dielectric constant of the solvent is low, the molecular weight distribution becomes broad, and when the dielectric constant of the solvent is large, the polymerization rate decreases.

As an organic solvent, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane are preferable from a viewpoint of the balance of polymerization activity and solubility. In addition, considering the viscosity of the obtained polymerization solution or the ease of heat removal, the concentration of the copolymer in the polymerization solution becomes 1 wt% to 90 wt%, preferably 10 wt% to 80 wt%, at the end of the polymerization. It is better to change the amount of solvent to 20wt% ~ 70wt%. When the concentration is less than 1 wt%, the cost is increased due to the low polymerization efficiency, and if it exceeds 90 wt%, the molecular weight and molecular weight distribution increase, resulting in a decrease in molding processability.

The polymerization reaction temperature is preferably 20 ° C to 120 ° C, and more preferably 40 ° C to 100 ° C. If the polymerization temperature is too high, the selectivity of the reaction is reduced, which causes problems such as an increase in molecular weight distribution or generation of gels. If the polymerization temperature is too low, the catalyst activity significantly decreases, and a large amount of catalyst must be added.

After the polymerization reaction is stopped, the method of recovering the copolymer is not particularly limited, For example, a generally used method such as a stripping method or precipitation using a poor solvent may be used.

According to the production method of the present invention, the terminally modified soluble polyfunctional vinyl aromatic copolymer of the present invention can be advantageously obtained.

Next, a first aspect of the curable composition of the present invention will be described. The hardening composition of this first aspect is useful as a substrate material in the field of advanced electronic equipment, for example, an electrical insulation material or a material facing a laminated body.

The hardening composition of the first aspect contains a terminally modified soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (also referred to as a radical polymerization catalyst) (XB). As the radical polymerization initiator (XB), for example, the resin composition of the present invention hardens by a cross-linking reaction by means such as heating as described later, but in order to reduce the reaction temperature at this time or promote the cross-linking of unsaturated groups The double-strand reaction can be used by containing a radical polymerization initiator (XB). Based on the sum of the (XA) component and the (XB) component, the amount of the radical polymerization initiator used for this purpose is 0.01 wt% to 10 wt%, preferably 0.1 wt% to 8 wt%. Since a radical polymerization initiator is a radical polymerization catalyst, it is hereinafter represented by a radical polymerization initiator.

As a radical polymerization initiator, a well-known thing can be used. Typical examples include benzamyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 2,5-dimethyl -2,5-di (third butyl peroxide) hexyne-3, bis-third butyl peroxide, third butylcumyl peroxide, α, α'-bis (peroxide Tributyl-m-isopropyl) benzene, 2,5-dimethyl-2,5-bis (third butyl peroxide) hexane, dicumyl peroxide, di-peroxy isophthalate Tert-butyl ester, benzene peroxide Third butyl formate, 2,2-bis (third butyl peroxide) butane, 2,2-bis (third butyl peroxide) octane, 2,5-dimethyl-2,5- Peroxides such as bis (benzylidene peroxide) hexane, bis (trimethylsilyl) peroxide, trimethylsilyl triphenylsilyl peroxide, but are not limited to these Oxide. In addition, although 2,3-dimethyl-2,3-diphenylbutane is not a peroxide, it can also be used as a radical polymerization initiator (or polymerization catalyst). However, the catalyst and radical polymerization initiator used for curing the present resin composition are not limited to these examples.

If the blending amount of the radical polymerization initiator is in the range of 0.01 to 10 parts by weight with respect to the terminally modified soluble polyfunctional vinyl aromatic copolymer (XA), the curing reaction proceeds well without hindering the curing reaction. reaction.

In addition, in the curable composition containing a terminally modified soluble polyfunctional vinyl aromatic copolymer (XA), if necessary, a terminally modified soluble polyfunctional vinyl aromatic copolymer (XA) may be blended with the terminally modified soluble polyfunctional vinyl aromatic copolymer ( XA) Other polymerizable monomers copolymerized and hardened.

A copolymerizable polymerizable monomer may be a known one. Typical examples include styrene, styrene dimer, α-methylstyrene, α-methylstyrene dimer, divinylbenzene, vinyltoluene, and tert-butyl Styrene, chlorostyrene, dibromostyrene, vinylnaphthalene, vinylbiphenyl, fluorene, divinylbenzyl ether, allylphenyl ether, and the like.

In addition, in the curable composition containing the terminally modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention, known thermosetting resins such as vinyl ester resin and polyvinyl benzyl can also be blended. Base resin, unsaturated polyester resin, Hardened vinyl resin, modified polyphenylene ether resin, maleimide resin, epoxy resin, polycyanate resin, phenol resin, etc., or known thermoplastic resins such as polystyrene, polybenzene Ethers, polyethers, imines, polyethers, polyphenylene sulfide (PPS) resins, polycyclopentadiene resins, polycycloolefin hydroxyl resins, etc., or known thermoplastic elastomers, such as styrene- Ethylene-propylene copolymer, styrene-ethylene-butene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, Hydrogenated styrene-isoprene copolymers and the like, or rubbers such as polybutadiene and polyisoprene.

The curable composition of the present invention may also be contained in a curable composition containing a terminally modified soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (XB). The modified polyphenylene ether (XC) represented by (7), in particular, a modified polyphenylene ether (XC) containing a group having at least one polymerizable unsaturated double bond at the terminal, such as a phenolic hydroxyl group, a vinyl group, and a (meth) acrylic group Phenyl ether (XC). The terminal modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention has good compatibility with the modified polyphenylene ether (XC), and overcomes the decline in reliability accompanying the decline in compatibility. One problem is that it exhibits improved characteristics such as low dielectric properties and toughness, and moldability and interlayer peel strength with arbitrary blending.

In the formula (7), m represents 1 or 2, and L represents a polyphenylene ether chain represented by the following formula (8). M represents a hydrogen atom and a group represented by the following formula (9). When m is 1, M is not a hydrogen atom, and when m is 2, at least one of the two Ms is not a hydrogen atom. When m is 1, T represents a hydrogen atom, and when m is 2, T represents an alkylene group, a group represented by the following formula (10) or formula (11).

In formula (8), n represents a positive integer of 50 or less, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a methylamino group, and an alkylcarbonyl group. , Alkenylcarbonyl, or alkynylcarbonyl.

In the formula (9), X is an organic group having 1 or more carbon atoms, and may include an oxygen atom. Y is vinyl. j represents an integer of 0 or 1.

In Formula (10), R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a methylamino group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. .

In formula (11), R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a methylamino group, Alkylcarbonyl, alkenylcarbonyl, or alkynylcarbonyl. F is a linear, branched, or cyclic hydrocarbon group having a carbon number of 20 or less when the carbon number is 0.

The modified polyphenylene ether represented by the formula (7) is one in which m in the formula (7) represents 1 or 2. That is, specifically, the modified polyphenylene ether represented by Formula (7) is a modified polyphenylene ether represented by T-L-M or ML-T-L-M.

In addition, L represents a polyphenylene ether chain represented by formula (8). In Formula (8), n represents a positive integer of 50 or less. R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independent. That is, R ⁵ , R ⁶ , R ⁷ , and R ⁸ may each be the same group or different groups. R ⁵ , R ⁶ , R ⁷ , and R ⁸ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a methylamino group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferred.

In addition, M represents a hydrogen atom and a group represented by formula (9). In addition, when M and m are 1, that is, when the modified polyphenylene ether is T-L-M, it is not a hydrogen atom, and represents a group represented by formula (9). In addition, when M is 2 and m, that is, when the modified polyphenylene ether is MTLLM, at least one of the two Ms is not a hydrogen atom, for reasons of heat resistance and toughness of the hardened material. It is preferable that both M are groups represented by formula (9).

In addition, when T is 1 in m, that is, when the modified polyphenylene ether is T-L-M, it represents a hydrogen atom. The modified polyphenylene ether represented by T-L-M is a modified polyphenylene ether represented by H-L-M. When T and m are 2, that is, when the modified polyphenylene ether is M-L-T-L-M, it represents an alkylene group, a group represented by the formula (10), or a group represented by the formula (11). Among them, for reasons of the toughness of the hardened material and the solubility of the modified polyphenylene ether, m is preferably 2, T is an alkylene, more preferably m is 2, and T is 2,2-propane. .

In formula (10), R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a methylamino group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynyl group. Carbonyl. R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ may each be the same group or different groups.

Specific examples of the functional groups listed in R ⁵ to R ²¹ include the following groups.

The alkyl group is not particularly limited. For example, an alkyl group having 1 to 18 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred. Specific examples include methyl, ethyl, propyl, hexyl, and decyl.

The alkenyl group is not particularly limited. For example, an alkenyl group having 2 to 18 carbon atoms is preferred, and an alkenyl group having 2 to 10 carbon atoms is more preferred. Specific examples include vinyl, allyl, and 3-butenyl.

The alkynyl group is not particularly limited. For example, an alkynyl group having 2 to 18 carbon atoms is preferred, and an alkynyl group having 2 to 10 carbon atoms is more preferred. Specific examples include ethynyl and prop-2-yn-1-yl (propargyl).

The alkylcarbonyl group is not particularly limited as long as it is an alkyl-substituted carbonyl group. For example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferred, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferred. Specifically, for example, ethenyl, propionyl, butylfluorenyl, isobutylfluorenyl, trimethylethylfluorenyl, hexamethylene, octyl, and cyclohexylcarbonyl are mentioned.

The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group. For example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferred, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferred. Specific examples include acrylfluorenyl, methacrylfluorenyl, and butenefluorenyl.

The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group. For example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferred, and a alkynylcarbonyl group having 3 to 10 carbon atoms is more preferred. Alkynylcarbonyl. Specific examples thereof include propargyl and the like.

In addition, the number average molecular weight of the modified polyphenylene ether is not particularly limited, but is preferably 800 to 7000, and more preferably 1,000 to 5000. The best is 1000 ~ 3000. In addition, as described above, n is a positive integer of 50 or less, but it is preferable that the number-average molecular weight of the modified polyphenylene ether is a value within such a range. Specifically, it is preferably 1 to 50. Here, the number-average molecular weight may be measured by a general molecular weight measurement method, and specifically, a value measured using a gel permeation chromatography (GPC) or the like may be mentioned.

When the number average molecular weight of the modified polyphenylene ether is within such a range, the toughness and formability of the cured product of the obtained curable composition will be higher. The reason is that if the number average molecular weight of the modified polyphenylene ether falls within this range, the molecular weight is relatively low, and therefore the toughness is improved while the fluidity is improved. When a general polyphenylene ether uses such a low molecular weight, there exists a tendency for the heat resistance and toughness of hardened | cured material to fall. However, since the modified polyphenylene ether used in this embodiment has a polymerizable unsaturated double bond at the terminal, the modified polyphenylene ether is hardened together with the vinyl-based heat-crosslinkable curable resin to modify the polyphenylene ether. The cross-linking with the heat-crosslinkable curable resin is suitably performed, and a heat-resistant material having high enough heat resistance and toughness can be obtained. Thereby, the hardened | cured material of the obtained hardenable composition can obtain the thing excellent in both heat resistance and toughness.

For the reason of improving the adhesion reliability between dissimilar materials, the hardenable composition of the present invention is also a suitable embodiment in which the hardenable composition is as follows. The hardenable composition is characterized in that it includes terminal modification. Hardening group of soluble polyfunctional vinyl aromatic copolymer (XA) and radical polymerization initiator (XB) The product contains epoxy resin (XD) and hardener (XE).

The epoxy resin as the (XD) component is not particularly limited. As the epoxy resin, it is preferable to use an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, and one molecule in one molecule. One or more of epoxy resins having two or more epoxy groups and cyanurate structures and / or one or more epoxy resins having two or more epoxy groups and alicyclic structures in one molecule Epoxy. The component (XD) is more preferably selected from the group consisting of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, an alkylphenol novolac epoxy resin, and xylylene modification. Phenolic novolac epoxy resin, xylyl modified alkylphenol novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, triglycidyl One or more epoxy resins in the group consisting of isocyanurate, cyclohexane epoxy resin, and adamantane epoxy resin.

Examples of the bisphenol F-type epoxy resin used as the (XD) component include a ring containing 4,4'-methylenebis (2,6-dimethylphenol) as a main component. Epoxy resin, epoxy resin containing 4,4'-methylenebis (2,3,6-trimethylphenol) as a main component, epoxy resin containing 4,4'-methylenebisphenol Diglycidyl ether as the main component of the epoxy resin. Among them, epoxy resins containing diglycidyl ether of 4,4′-methylenebis (2,6-dimethylphenol) as a main component are preferred. The bisphenol F-type epoxy resin can be obtained in the form of a commercially available product under the trade name YSLV-80XY manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.

Examples of the biphenyl type epoxy resin include 4,4'-diglycidyl biphenyl and 4,4'-diglycidyl-3,3 ', 5,5'-tetramethylbiphenyl. Epoxy. As The biphenyl-type epoxy resin can be obtained in the form of commercially available products under the trade names YX-4000 and YL-6121H manufactured by Mitsubishi Chemical Corporation.

Examples of the dicyclopentadiene-type epoxy resin include dicyclopentadiene dioxide and a phenol novolac epoxy monomer having a dicyclopentadiene skeleton.

Examples of the naphthalene-type epoxy resin include 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-diglycidyl naphthalene, triglycidyl naphthalene, and 1,2,5,6-tetraglycidyl naphthalene, naphthol. Aralkyl-type epoxy resin, naphthalene skeleton modified cresol novolac Modified epoxy resin, methoxynaphthalene modified cresol novolac epoxy resin, modified naphthalene ether epoxy resin, modified naphthalene epoxy resin, etc. .

Examples of the adamantane-type epoxy resin include 1- (2,4-diglycidyloxyphenyl) adamantane and 1- (2,3,4-triglycidyloxyphenyl) adamantane. , 1,3-bis (2,4-diglycidyloxyphenyl) adamantane, 1,3-bis (2,3,4-triglycidyloxyphenyl) adamantane, 2,2-bis (2,4-Diglycidyloxyphenyl) adamantane, 1- (2,3,4-trihydroxyphenyl) adamantane, 1,3-bis (2,4-dihydroxyphenyl) adamantane , 1,3-bis (2,3,4-trihydroxyphenyl) adamantane, and 2,2-bis (2,4-dihydroxyphenyl) adamantane.

Among the epoxy resins, from the viewpoints of compatibility with the (XA) component, dielectric characteristics, and small warpage of the molded product, bisphenol F-type epoxy resins, alkyl groups can be suitably used. Phenolic novolac epoxy resin, xylylene modified phenol novolac epoxy resin, xylylene modified alkylphenol novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene ring Oxygen resin, naphthalene type epoxy resin, triglycidyl isocyanurate, cyclohexane type epoxy resin, adamantane type epoxy tree fat.

The weight average molecular weight (Mw) of the epoxy resin used as the (XD) component is preferably less than 10,000. A more preferable Mw is 600 or less, and further more preferably 200 or more and 550 or less. When the Mw is less than 200, the volatility of the component tends to be high, and the handleability of the cast film tends to deteriorate. On the other hand, if Mw exceeds 10,000, there is a cast film. The sheet is easy to harden and become brittle, and cast film. The cured product of the sheet tends to have reduced adhesiveness.

The lower limit is preferably 5 parts by weight and the upper limit is 100 parts by weight based on 100 parts by weight of the (XA) component. More preferably, the lower limit of the content of the (XD) component is 10 parts by weight based on 100 parts by weight of the (XA) component. On the other hand, a more preferable upper limit is 80 weight part, and a more preferable upper limit is 60 weight part. If the content of the (XD) component satisfies the preferred lower limit, the cast film can be further improved. Adhesion of hardened sheet. If the content of the (XD) component satisfies the preferable upper limit, the cast film is in an unhardened state. The workability of the sheet is further improved, the adhesion with the glass cloth is improved, and the reliability is improved.

The curing agent of the (XE) component is preferably a phenol resin or an acid anhydride having an aromatic skeleton or an alicyclic skeleton, a hydrogenated product of the acid anhydride, a modified product of the acid anhydride, a hydroxyl-terminated polyphenylene ether oligomer, and an active ester. Compound. By using these preferable hardeners, a hardenable composition which becomes a hardened | cured material excellent in the balance of heat resistance, moisture resistance, and dielectric characteristics can be obtained.

The phenol resin used as a hardener of (XE) component is not specifically limited. Specific examples of the phenol resin include phenol novolac, o-cresol novolac, P-cresol novolac, third butylphenol novolac, dicyclopentadiene cresol, poly-p-vinylphenol, bisphenol A novolac, phenol aralkyl resin, naphthol aralkyl resin, biphenyl Phenol novolac resin, biphenyl naphthol novolac resin, decalin modified novolac, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, and poly (di- P-hydroxyphenyl) methane and the like. Among them, a phenol resin having a melamine skeleton, a phenol resin having a triazine skeleton, or a phenol resin having an allyl group is preferred because the flexibility and flame retardancy of the insulating sheet can be further improved.

Examples of commercially available phenol resins include MEH-8005, MEH-8010, and NEH-8015 (all of which are manufactured by Meiwa Chemical Co., Ltd.), YLH903 (made by Japan Epoxy Resins), LA -7052, LA-7054, LA-77751, LA-1356, and LA-3018-50P (the above are manufactured by DIC), and PS6313 and PS6492 (made by Qunrong Chemical Co., Ltd.).

The structure of the acid anhydride having an aromatic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride used as a curing agent for the (XE) component is not particularly limited. Examples of the acid anhydride having an aromatic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride include a styrene / maleic anhydride copolymer, benzophenone tetracarboxylic anhydride, pyromellitic anhydride, Trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenylethynyl phthalic anhydride, glycerol bis (anhydrotrimellitic acid ester) monoacetate, ethylene glycol bis (anhydrous Trimellitic acid ester), methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride, methylnadic anhydride, trialkyltetrahydro Phthalic anhydride, or an acid anhydride having a dicyclopentadiene skeleton or a modification of the acid anhydride Quality and so on.

Examples of the commercially available product of the acid anhydride having an aromatic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride include: SMA RESIN EF30, SMA RESIN EF40, SMA RESIN EF60, and SMA RESIN EF80 (Made by Sartomer. Japan), ODPA-M and PEPA (above are manufactured by Manac), RIKACID MTA-10, RIKACID MTA-15, RIKACID TMTA, RIKACID TMEG-100, RIKACID TMEG -200, RIKACID TMEG-300, RIKACID TMEG-500, RIKACID TMEG-S, RIKACID TH, RIKACID HT-1A, RIKACID HH, RIKACID MH-700, RIKACID MT-500, RIKACID DSDA, and RIKACID TDA-100 (the above are all (Manufactured by New Japan Physicochemical Co., Ltd.), and EPICLON B4400, EPICLON B650, and EPICLON B570 (all of which are manufactured by Dickson).

The acid anhydride having an alicyclic skeleton, the hydride of the acid anhydride, or a modified product of the acid anhydride is preferably an acid anhydride having a polyalicyclic skeleton, a hydride of the acid anhydride, or a modified product of the acid anhydride, or a terpene An acid anhydride having an alicyclic skeleton obtained by an addition reaction of a system compound with maleic anhydride, a hydride of the acid anhydride, or a modified product of the acid anhydride. In this case, the flexibility, moisture resistance, or adhesion of the insulating sheet can be further improved. Examples of the acid anhydride having an alicyclic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride include methyl nadic acid anhydride, an acid anhydride having a dicyclopentadiene skeleton, or a modified product of the acid anhydride. Wait.

As the acid anhydride having an alicyclic skeleton, a hydride of the acid anhydride, or the Commercially available products of modified anhydrides include: RIKACID HNA and RIKACID HNA-100 (all of which are manufactured by Shin Nippon Chemical Co., Ltd.), and EPICURE YH306, EPICURE YH307, EPICURE YH308H, and EPICURE YH309 (the above are all Japanese epoxy resins) Company)).

As the (XE) component, a hydroxyl-terminated polyphenylene ether oligomer may also be used. Examples thereof include a hydroxyl-terminated polyphenylene ether oligomer represented by the following formula (12).

In the formula (12), p represents 1 or 2, E represents a polyphenylene ether chain represented by the following formula (13), G represents a hydrogen atom, and p represents an integer of 1 or 2. When p is 1, V represents a hydrogen atom, and when p is 2, V represents an alkylene group, a group represented by the following formula (14) or (15).

In Formula (13), q represents a positive integer of 50 or less, and R ²² , R ²³ , R ²⁴ , and R ²⁵ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a methylamino group, and an alkylcarbonyl group. , Alkenylcarbonyl, or alkynylcarbonyl.

(In formula (14), R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a methylamino group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynyl group. (Carbonyl)

In formula (15), R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a methylamino group, Alkylcarbonyl, alkenylcarbonyl, or alkynylcarbonyl. F is a linear, branched, or cyclic hydrocarbon group having a carbon number of 20 or less when the carbon number is 0.

As the (XE) component, an active ester compound can also be used. It is only required to have an active ester group, but in the present invention, a compound having at least two active ester groups in the molecule is preferred.

The active ester compound used as the (XE) component is preferably formed by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound from the viewpoint of heat resistance and the like. The active ester compound obtained is more preferably an activity obtained by reacting a carboxylic acid compound with one or two or more selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound. The ester compound is particularly preferably an aromatic compound obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group and having at least two active ester groups in the molecule. The active ester compound used as the (XE) component may be linear or multi-branched. If the case where the active ester compound is derived from a compound having at least two carboxylic acids in the molecule is exemplified, when such an active ester compound has at least two in the molecule When a carboxylic acid compound contains an aliphatic chain, compatibility with an epoxy resin can be improved, and when it has an aromatic ring, heat resistance can be improved.

Specific examples of the carboxylic acid compound used to form the active ester compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid. Formic acid, pyromellitic acid, etc. Among these, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and phthalic acid is more preferred. Dicarboxylic acid, isophthalic acid, and terephthalic acid, and even more preferably isophthalic acid and terephthalic acid.

Specific examples of the thiocarboxylic acid compound used to form the active ester compound include thioacetic acid and thiobenzoic acid.

Specific examples of the phenol compound and naphthol compound used to form the active ester compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthaloline, and methylated bis Phenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-bis Hydroxynaphthalene, 1,6-Dihydroxynaphthalene, 2,6-Dihydroxynaphthalene, Dihydroxybenzophenone, Trihydroxybenzophenone, Tetrahydroxybenzophenone, Pyrogallol, Pyrogallol, Diamine Cyclopentadienyl diphenol, phenol novolac, etc. Among these, from the viewpoints of heat resistance and solubility, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, phenol novolac, more preferably dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone , Dicyclopentadienyl diphenol, phenol novolac, and more preferably dicyclopentadienyl diphenol, phenol novolac.

Specific examples of the thiol compound used to form the active ester compound include benzenedithiol, triazinedithiol, and the like.

As the active ester compound, for example, an active ester compound disclosed in Japanese Patent Laid-Open No. 2002-12650 and Japanese Patent Laid-Open No. 2004-277460 or a commercially available active ester compound can be used. Examples of commercially available active ester compounds include: trade names "EXB9451, EXB9460, EXB9460S, HPC-8000-65T" (above, manufactured by Di Edison), trade names "DC808" (manufactured by Japan Epoxy Resin Company), Trade name "YLH1026" (Japan Epoxy Resin Company Manufacturing) etc.

The manufacturing method of an active ester compound is not specifically limited, It can manufacture by a well-known method, For example, it can obtain by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound, and a hydroxyl compound and / or a thiol compound.

The blending amount of the active ester compound (XE) in the curable composition of the present invention is preferably 20 to 120 parts by weight, and more preferably 40 to 100 parts by weight based on 100 parts by weight of the epoxy resin (XD). Parts, more preferably in the range of 50 parts by weight to 90 parts by weight. By setting the blending amount of the active ester compound (XE) within the above range, it is possible to improve the dielectric characteristics, heat resistance, and linear expansion coefficient of the cured product.

As the curing agent used as the (XE) component, from the viewpoints of compatibility with the (XA) component of the present invention, moisture resistance, and adhesiveness, preferred are auto-cresol novolac and p-cresol novolac. Varnish, tertiary butylphenol novolac, dicyclopentadiene cresol, poly-p-vinylphenol, xylylene modified novolac, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxybenzene) Group) methane, poly (di-p-hydroxyphenyl) methane, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, or an anhydride having a dicyclopentadiene skeleton or a modified product of the anhydride, a hydroxyl group The terminal polyphenylene ether oligomer or active ester compound is selected.

The use of fused silica, crystalline silica, alumina, silicon nitride, and aluminum nitride in the curable composition containing a terminally modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention Inorganic fillers such as flame retardants such as decabromodiphenylethane and brominated polystyrene are particularly useful as materials for electrical parts or electronic parts that require dielectric properties, flame retardancy, or heat resistance. , In particular, varnishes for semiconductor sealing materials and circuit boards.

The varnish for a circuit board material can be produced by dissolving the curable composition of the present invention in an organic solvent such as toluene, xylene, tetrahydrofuran, or dioxane. In addition, the circuit board material specifically includes a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.

The cured product obtained by curing the curable composition containing the terminally modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention can be used as a molded article, a laminate, a casting, an adhesive, a coating film, and a film. . For example, the hardened material of the semiconductor sealing material is a cast product or a molded product. As a method for obtaining the hardened product of the application, the compound can be molded by casting, a transfer molding machine, an injection molding machine, or the like, and further heated at 80 ° C. It is heated at ~ 230 ° C for 0.5 to 10 hours to obtain a hardened body. In addition, the cured product of the circuit board varnish is a laminate, and as a method of obtaining the cured product, the circuit board varnish may be impregnated with glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, or the like. The material is heated and dried to obtain a prepreg, and then the prepregs are separately laminated with each other or with a metal foil such as a copper foil, and are hot-pressed to obtain the cured product.

In addition, by blending inorganic high-dielectric powder such as barium titanate, or inorganic magnetic bodies such as ferrous iron, it is useful as a material for electronic parts, particularly as a material for high-frequency electronic parts.

In addition, similar to the hardened composite material described later, the hardenable composition of the present invention can be used by bonding it to a metal foil (including the meaning of a metal plate. The same applies hereinafter).

Then, the hardenable composite material of the hardenable composition of the present invention and The hardened body will be described. In order to increase mechanical strength and increase dimensional stability, a base material is added to a hardenable composite material formed of the hardenable composition of the present invention.

As such a substrate, a known substrate can be used. For example, various glass cloths such as gauze cloth, cloth, strand felt, and surface felt can be used individually, asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth. , Woven or non-woven fabrics obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, polybenzoxazole fibers, and synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, and acrylic fibers Woven or non-woven fabrics, natural fiber cloths such as cotton, burlap, felt, carbon fiber cloth, kraft paper, cotton paper, paper-glass mixed fiber and other natural cellulose cloths, papers, etc., or a combination of two or more .

In the hardenable composite material, the proportion of the substrate is 5wt% to 90wt%, preferably 10wt% to 80wt%, and more preferably 20wt% to 70wt%. If the base material is less than 5 wt%, the dimensional stability or strength of the composite material after curing is insufficient, and if the base material is more than 90 wt%, the dielectric properties of the composite material are poor and unsatisfactory.

In the curable composite material of the present invention, a coupling agent may be used as necessary in order to improve the adhesion at the interface between the resin and the substrate. As the coupling agent, general coupling agents such as a silane coupling agent, a titanate coupling agent, an aluminum-based coupling agent, and an aluminum-zirconium coupling agent can be used.

As a method for producing the curable composite material of the present invention, for example, a method of uniformly dissolving or dispersing the curable composition of the present invention and other components as necessary in a solvent such as the aromatic system, ketone system, or the like can be cited. After being impregnated into the base material or a mixed solvent thereof, it is dried. Impregnation is performed by dipping, coating, or the like. Impregnation can be repeated as many times as needed. In addition, composition or concentration can also be used at this time. Repeat the impregnation with various solutions of different degrees, and finally adjust to the desired resin composition and resin amount.

The hardened composite material of the present invention is hardened by a method such as heating to obtain a hardened composite material. The manufacturing method is not particularly limited. For example, a plurality of hardenable composite materials can be superimposed and heat-cured while adhering between the layers under heat and pressure to obtain a hardened composite material having a desired thickness. In addition, a hardened composite material that has been adhesively hardened once can be combined with a hardenable composite material to obtain a hardened composite material with a new layer structure. Laminated molding and hardening are usually performed simultaneously by hot pressing or the like, but both of them may be performed separately. That is, the unhardened or semi-hardened composite material obtained by laminating in advance can be treated by heat treatment or other methods to harden it.

Forming and curing can be performed at temperature: 80 ℃ ~ 300 ℃, pressure: 0.1kg / cm ² ~ 1000kg / cm ² , time: 1 minute ~ 10 hours, more preferably temperature: 150 ℃ ~ 250 ℃, pressure 1kg / cm ² to 500 kg / cm ² , time: 1 minute to 5 hours.

The laminated body of the present invention refers to a layer including a layer of the hardened composite material of the present invention and a layer of a metal foil. Examples of the metal foil used herein include copper foil and aluminum foil. The thickness is not particularly limited, but is in a range of 3 μm to 200 μm, and more preferably in a range of 3 μm to 105 μm.

As a method for producing the laminated body of the present invention, for example, a method can be mentioned in which the above-mentioned hardenable composite material and metal foil obtained from the hardenable composition and the base material of the present invention are used in a layer structure corresponding to the purpose. Laminated and heated with Under pressure, the layers are thermally cured while adhering to each other. In the laminated body of the curable composition of this invention, a hardening composite material and a metal foil are laminated | stacked by arbitrary layer constitutions. Metal foil can be used as a surface layer or an intermediate layer. In addition to the above, multilayering may be performed by repeating the lamination and curing multiple times.

Adhesives can also be used for adhesion to metal foil. Examples of the adhesive include epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesives, but are not particularly limited to these adhesives. The laminated molding and hardening can be performed under the same conditions as in the production of the hardened composite material of the present invention.

The film of this invention is a thing formed by shape | molding the curable composition of this invention into a film form. The thickness is not particularly limited, but it is in a range of 3 μm to 200 μm, and more preferably in a range of 5 μm to 100 μm.

The method for producing the film of the present invention is not particularly limited, and examples thereof include a method of uniformly dissolving or dispersing the curable composition and other components as necessary in an aromatic or ketone-based solvent or the like The mixed solvent is applied to a resin film such as a polyethylene terephthalate (PET) film and then dried. The coating can be repeated as many times as necessary. In addition, at this time, multiple solutions with different compositions or concentrations can be used for repeated coating, and finally adjusted to the desired resin composition and resin amount.

The metal foil with a resin of this invention means the thing containing the curable composition of this invention and a metal foil. Examples of the metal foil used herein include copper foil and aluminum foil. The thickness is not particularly limited, but it is in a range of 3 μm to 200 μm, and more preferably in a range of 5 μm to 105 μm.

The method for producing the resin-containing metal foil of the present invention is not particularly limited, and examples thereof include a method of uniformly dissolving or dispersing a curable composition and other components as needed in an aromatic system, a ketone system, or the like. In a solvent or a mixed solvent thereof, it is coated on a metal foil and then dried. The coating can be repeated as many times as necessary. In addition, at this time, multiple solutions with different compositions or concentrations can be used for repeated coating, and finally adjusted to the desired resin composition and resin amount.

The modified terminal soluble polyfunctional vinyl aromatic copolymer of the present invention can be processed into formed materials, sheets or films for use in the electrical industry and space. In fields such as the aircraft industry, it can be used for low-dielectric materials, insulating materials, heat-resistant materials, structural materials, and the like that can satisfy characteristics such as low dielectric constant, low water absorption, and high heat resistance. In particular, it can be used as a single-sided, double-sided, multi-layer printed substrate, flexible printed substrate, build-up substrate, and the like. Furthermore, it can be applied to semiconductor-related materials or optical materials, and can also be applied to coatings, photosensitive materials, adhesives, sewage treatment agents, heavy metal capture agents, ion exchange resins, antistatic agents, antioxidants, antifog agents, and anti-fog agents. Rust inhibitors, antiseptics, bactericides, insecticides, medical materials, coagulants, surfactants, lubricants, solid fuel adhesives, conductive treatment agents, etc.

In addition, the hardenable composition of the present invention has high dielectric properties (low dielectric constant, low dielectric loss tangent) after severe thermal history, and has high adhesion reliability even under harsh environments. The cured product has excellent resin fluidity, low linear expansion, and excellent wiring flatness. Therefore, Yu Electric. Electronics industry, space. In the fields of the aircraft industry and other fields, hardened molded products corresponding to the miniaturization and thinness that have been strongly demanded in recent years and without forming defects such as warpage can be provided as dielectric materials, insulation Edge materials, heat-resistant materials, structural materials, etc. Furthermore, since wiring flatness is excellent and adhesiveness with a different material is excellent, a resin composition, a cured product, or a material containing the same can be realized with excellent reliability.

Hereinafter, the second aspect of the curable resin composition of the present invention will be described. The curable resin composition of the second aspect is particularly useful as a material for an optical waveguide.

The curable resin composition of the second aspect of the present invention contains (A) component, (B) component, and (C) component as essential components. Here, the component (A) is a terminally modified soluble polyfunctional vinyl aromatic copolymer, the component (B) is one or more vinyl compounds having one or more unsaturated groups in the molecule, and the (C) component is Free radical polymerization initiator.

The terminally modified soluble polyfunctional vinyl aromatic copolymer used as the component (A) is as described in detail.

Next, (B) component is demonstrated in the curable resin composition of a 2nd aspect.

The component (B) is one or more vinyl compounds having one or more unsaturated groups in the molecule. In addition, the component (B) is not the same as the component (A). That is, the component (A) is not treated as the component (B).

Here, the vinyl compound may be any polymerizable compound having an olefinic double bond (unsaturated group). The position of the unsaturated group is not limited, and the number of unsaturated groups may be one or more. Each. Hereinafter, the unsaturated group is also referred to as a vinyl group. The vinyl group of the component (B) can be copolymerized with the vinyl group of the component (A).

As a preferable (B) component, there are 1 or more (methyl) groups in a molecule | numerator. One or more (meth) acrylic esters of acrylfluorenyl. Furthermore, there are one or more types of (meth) acrylates having a hydroxyl group and / or a carboxyl group.

The (meth) acrylate used as the (B) component is not particularly limited as long as it has one or more (meth) acrylfluorenyl groups in the molecule, and any one can be used.

Examples of the (meth) acrylate compound having one (meth) acrylfluorenyl group in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, (meth) Butoxyethyl acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate , Nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, fourteen (meth) acrylate Ester, pentadecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, methoxypolyethylene glycol (methyl ) Aliphatic (meth) acrylates such as acrylate, ethoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate ; (A ) Cyclohexyl acrylate, cyclopentyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, etc. (Meth) acrylates; phenyl (meth) acrylate, benzyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate , Phenoxyethyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 1-naphthyloxy (meth) acrylate Ethyl ester, 2-naphthyloxy (meth) acrylate Aromatic (methyl) such as ethyl ester, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate ) Acrylate; 2-tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloxyethylhexahydrophthalimide, 2- (meth) acryloxyethyl -N-carbazole and other heterocyclic (meth) acrylates.

Examples of the polyfunctional (meth) acrylate having two or more (meth) acrylfluorene groups in the molecule include 1,4-butanediol di (meth) acrylate, and 1,6- Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecanedimethanol (meth) acrylate, bisphenol A polyethoxybis (methyl) ) Acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, (meth) acrylate three Trimethylolpropane trioxyethyl, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (propenyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (methyl) Base) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxytrimethylacetic acid neopentyl glycol di ( Acrylate), di (meth) acrylate of ε-caprolactone adduct of hydroxytrimethylacetate neopentyl glycol (e.g. KAYARAD HX- manufactured by Nippon Kayaku Co., Ltd.) 220, KAYARAD (HX-620, etc.), trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, di-trimethylol Monomers such as propane tetra (meth) acrylate.

Among these, from the viewpoint of transparency and heat resistance, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate are preferred. Esters, aliphatic (meth) acrylates such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; alicyclic (meth) acrylates; aromatic (meth) acrylates; Heterocyclic (meth) acrylate.

These compounds can be used alone or in combination of two or more.

When the curable resin composition of the present invention is a curable resin composition for forming a waveguide, it is preferred that the curable resin composition contains a structural unit represented by the general formula (16) or the general formula (17). A vinyl compound or a curable vinyl polymer produced from the vinyl compound is used as the component (B).

In the general formula (16) or (17), R ⁵ and R ⁸ represent a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R ⁶ and R ⁹ represent A hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. X ¹ and X ² represent two carbon atoms having 1 to 20 carbon atoms that may contain one or more bonds selected from the group consisting of a single bond, or an ester bond, an ether bond, a thioester bond, a thioether bond, and a amide bond. Valent organic radical.

The vinyl compound having a structural unit represented by the general formula (16) or the general formula (17) or a curable vinyl polymer derived from the vinyl compound is preferably a (meth) acrylate or (Meth) acrylate polymer.

Here, the curable vinyl polymer may be obtained by homopolymerizing or copolymerizing the vinyl compound and having at least one vinyl group.

In the general formula (16) or the general formula (17), there is no particular limitation on the divalent organic group when X ¹ and X ² are divalent organic groups having 1 to 20 carbon atoms. Divalent organic groups such as alkyl, cycloalkyl, phenyl, phenyl, polyether, polysiloxane, carbonyl, ester, amido, carbamate, etc. These may be halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, carbonyl groups, formamyl groups, ester groups, amido groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, silanes And silyloxy.

Among these, from the viewpoints of transparency and heat resistance, preferred are alkylene, cycloalkyl, phenyl, and biphenyl.

When R ⁷ , R ⁶ , and R ⁹ are monovalent organic groups having 1 to 20 carbon atoms, the organic group is not particularly limited, and examples thereof include alkyl, cycloalkyl, aryl, aralkyl, and fluorene (-CO-R), ester (-CO-OR or -O-CO-R), amido (-CO-NR ₂ or -NR-CO-R) and other equivalent organic groups, these Can be selected from hydroxyl, halogen atom, alkyl, cycloalkyl, aryl, aralkyl, carbonyl, formamyl, ester, amido, alkoxy, aryloxy, alkylthio, arylthio, amine Group, silane group, silyloxy group, etc. are further substituted. Here, R is a hydrocarbon group.

Among these, an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group are preferable from a viewpoint of transparency and heat resistance.

When the (B) component is one or more (meth) acrylates having one or more (meth) acrylfluorenyl groups in the molecule, the (meth) acrylate is not particularly limited, and examples thereof include: ( Aliphatic (such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate) (Meth) acrylate, or 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, (meth) Acrylic 2- Aromatic (meth) acrylates such as hydroxy-3- (1-naphthyloxy) propyl ester and 2-hydroxy-3- (2-naphthyloxy) propyl (meth) acrylate.

Among these, from the viewpoints of transparency and heat resistance, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate are preferred. Aliphatic (meth) acrylates such as esters, or 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate And other aromatic (meth) acrylates.

These compounds can be used alone or in combination of two or more.

When the component (B) is a vinyl compound having a structural unit represented by the general formula (17) or a vinyl compound having a carboxyl group, the vinyl compounds are not particularly limited, and examples thereof include: (methyl ) Acrylic acid, crotonic acid, cinnamic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, mono (2- (meth) acryloxyethyl) succinic acid Acid ester, mono (2- (meth) acryloxyethyl) phthalate, mono (2- (meth) acryloxyethyl) isophthalate, mono (2 -(Meth) acryloxyethyl) terephthalate, mono (2- (meth) acryloxyethyl) tetrahydrophthalate, mono (2- (methyl) ) Propylene ethoxyethyl) hexahydrophthalate, mono (2- (meth) propylene ethoxyethyl) hexahydroisophthalate, mono (2- (meth) propylene (Ethoxyethyl) hexahydroterephthalate, ω-carboxy-polycaprolactone mono (meth) acrylate, 3-vinylbenzoic acid, 4-vinylbenzoic acid, and the like.

Among these, from the viewpoints of transparency, heat resistance, and solubility in an alkaline developer, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, Mono (2- (meth) acryloxyethyl) succinate, mono (2- (methyl) propane Alkyloxyethyl) tetrahydrophthalate, mono (2- (meth) acryloxyethyl) hexahydrophthalate, mono (2- (meth) acryl) (Oxyethyl) hexahydroisophthalate, mono (2- (meth) acryloxyethyl) hexahydroterephthalate.

Further, a vinyl compound having two or more carboxyl groups such as maleic anhydride and citraconic anhydride or a part of the carboxyl groups of the acid anhydride thereof may be partially esterified with an appropriate alcohol such as methanol, ethanol, and propanol, as appropriate. Made of vinyl compounds.

In addition, an acid anhydride of a vinyl compound having two or more carboxyl groups and a (meth) acrylic acid ester compound having one or more (meth) acrylfluorenyl groups in a molecule may be suitably used, and then methanol may be used. A vinyl compound obtained by partially esterifying an appropriate alcohol such as ethanol, propanol, or the like.

These compounds can be used alone or in combination of two or more.

In the curable resin composition for forming an optical waveguide, a hardened (meth) acrylate (B1) having a urethane bond and one or more (meth) acrylfluorenyl groups can be preferably used. (B) A vinyl compound as a component.

The hardening type (meth) acrylate (B1) is not particularly limited, and examples thereof include the following (1) to (4) (meth) acrylic acid urethane and the like.

(1) A (meth) acrylic acid urethane obtained by reacting a difunctional alcohol compound, a difunctional isocyanate compound, and a (meth) acrylate having a hydroxyl group.

(2) A (meth) acrylic acid urethane obtained by reacting a difunctional alcohol compound, a difunctional isocyanate compound, and a (meth) acrylate having an isocyanate group.

(3) A urethane (meth) acrylate obtained by reacting a polyfunctional isocyanate compound and a (meth) acrylate having a hydroxyl group.

(4) A urethane (meth) acrylate obtained by reacting a polyfunctional alcohol compound and a (meth) acrylate having an isocyanate group.

Among these, from the viewpoint of transparency and heat resistance, it is preferable that the molecule has at least one (methyl group) selected from the group consisting of an alicyclic structure, an aromatic ring structure, and a heterocyclic structure in its molecule. ) Urethane acrylate.

The difunctional alcohol compound, that is, the diol compound is not particularly limited, and examples thereof include a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, a polycaprolactone diol compound, and others Diol compounds and the like.

The polyether glycol compound is not particularly limited, and examples thereof include those selected from the group consisting of ethylene oxide, propylene oxide, isobutylene oxide, butyl glycidyl ether, butene-1-oxide, and 3 3,3-Dichloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, epoxycyclohexane, styrene oxide, phenyl glycidyl ether, glycidyl benzoate and other rings Polyether diol compound obtained by ring-opening (co) polymerization of at least one of the ether-like compounds; lipids such as cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F A polyether diol compound obtained by ring-opening addition of a cyclic diol compound and at least one selected from the cyclic ether compounds, or by causing hydroquinone, resorcinol, catechol, Polyether diol compounds obtained by ring-opening addition of bifunctional phenol compounds such as bisphenol A, bisphenol F, bisphenol AF, biphenol, and bisphenol, and at least one selected from the cyclic ether compounds. .

The polyester diol compound is not particularly limited, and examples thereof include malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, tetrahydrophthalic acid, and hexahydrophthalic acid. Difunctional carboxylic acid compounds such as dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, itaconic acid, and ethylene glycol, diethylene glycol, poly Ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, dibutylene glycol, polybutylene glycol, pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, hexanediol Polyester polyol compounds obtained by copolymerizing diol compounds such as alcohol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanedimethanol, and tricyclodecanedimethanol.

The polycarbonate diol compound is not particularly limited, and examples thereof include carbonyl dichloride, carbonyl trichloride, dialkyl carbonate, diaryl carbonate, and the like with ethylene glycol and diethyl carbonate. Glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, dibutyl glycol, polybutylene glycol, pentylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol Glycol compounds such as alcohol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F Polycarbonate diol compound and the like obtained by polymerization.

The polycaprolactone diol compound is not particularly limited, and examples thereof include ε-caprolactone and ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and butylene. Glycol, dibutanediol, polybutanediol, pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, hexanediol, heptanediol, octanediol, nonanediol Polycaprolactone diol compound obtained by copolymerizing diol compounds such as decanediol, cyclohexanedimethanol, and tricyclodecanedimethanol.

Examples of other diol compounds include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, dibutylene glycol, pentanediol, neopentyl glycol, and 3-methyl-1,5 -Aliphatic diol compounds such as pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol; cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenation Aliphatic diol compounds such as bisphenol F; modified diol compounds such as polybutadiene modified diol compounds, hydrogenated polybutadiene modified diol compounds, silicone modified diol compounds, and the like.

These diol compounds can be used alone or in combination of two or more.

The difunctional isocyanate compound is not particularly limited, and examples thereof include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and decamethylene. Aliphatic difunctional isocyanate compounds such as methyl diisocyanate, dodecyl diisocyanate; 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,5-bis (iso Cyanomethyl) norbornene, bis (4-isocyanatocyclohexyl) methane, 1,2-bis (4-isocyanatocyclohexyl) ethane, 2,2-bis (4-iso Cyclocyclohexyl) propane, 2,2-bis (4-isocyanatocyclohexyl) hexafluoropropane, dicycloheptane triisocyanate and other alicyclic difunctional isocyanate compounds; 2,4'-diphenyl Methane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylene Aromatic difunctional isocyanate compounds such as tolyl diisocyanate.

These compounds can be used alone or in combination of two or more.

The (meth) acrylate having a hydroxyl group is not particularly limited, Examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate Ester, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, 2-hydroxy- (meth) acrylate- Monofunctional (meth) acrylates such as 3- (1-naphthyloxy) propyl ester, 2-hydroxy-3- (2-naphthyloxy) propyl (meth) acrylate, and these ethoxylated bodies , These propoxylated bodies, these ethoxylated propoxylated bodies, and these caprolactone modified bodies; bis (2- (meth) acryloxyethyl)) ( Bifunctional (meth) acrylates such as 2-hydroxyethyl) isocyanurate, these ethoxylated bodies, these propoxylated bodies, these ethoxylated propoxylated And modified caprolactones; cyclohexanedimethanol epoxy di (meth) acrylate, tricyclodecanedimethanol epoxy di (meth) acrylate, hydrogenated bis Phenol A type epoxy di (meth) acrylate, hydrogenated bisphenol F type epoxy di (meth) acrylate, hydroquinone type epoxy bis (methyl) ) Acrylate, resorcinol epoxy di (meth) acrylate, catechol epoxy di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, Bisphenol F type epoxy di (meth) acrylate, Bisphenol AF type epoxy di (meth) acrylate, Biphenol type epoxy di (meth) acrylate, 茀 bisphenol type epoxy Difunctional epoxy (meth) acrylates such as di (meth) acrylate, isotricyanic acid monoallyl epoxy di (meth) acrylate, pentaerythritol tri (meth) acrylate, More than trifunctional (meth) acrylates such as dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, these ethoxylated bodies, these propoxylated bodies, the Some ethoxylated propoxylated bodies, and these caprolactone modified bodies; phenol novolac epoxy (meth) acrylate, cresol novolac epoxy poly (meth) acrylic Ester Trifunctional or higher epoxy (meth) acrylates such as polycyanate epoxy tri (meth) acrylates and the like.

These compounds can be used alone or in combination of two or more.

Here, the ethoxylated body, propoxylated body, and ethoxylated propoxylated body of (meth) acrylate means an alcohol compound or a phenol compound (for example, a monofunctional ( (Meth) acrylate; in the case of CH ₂ = CH (R ⁷ ) -COO-R ⁸ (where R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a monovalent organic group), represented by HO-R ⁸ ), An alcohol compound having a structure obtained by adding one or more ethylene oxides to the alcohol compound or a phenol compound, an alcohol compound having a structure obtained by adding one or more propylene oxides, or (Meth) acrylate obtained by using an alcohol compound having a structure of one or more ethylene oxide and propylene oxide as a raw material (for example, in the case of an ethoxylate, CH ₂ = CH ( R ⁷ ) -COO- (CH ₂ CH ₂ O) _q -R ⁸ (where q is an integer of 1 or more, and R ⁷ and R ⁸ are the same as described above)). The term “caprolactone modified body” refers to (meth) acrylic acid obtained by using an alcohol compound modified by using ε-caprolactone as a raw material of a (meth) acrylate as a raw material. Ester (for example, in the case of a caprolactone modifier of a monofunctional (meth) acrylate, from CH ₂ = CH (R ⁷ ) -COO-((CH ₂ ) ₅ COO) _q -R ⁸ (q , R ⁷ and R ⁸ are the same as described above).

The (meth) acrylate having an isocyanate group is not particularly limited, and examples thereof include N- (meth) acrylfluorenyl isocyanate, (meth) acryloxymethyl isocyanate, and 2- (formaldehyde) Group) acryloxyethyl isocyanate, 2- (meth) acryloxyethoxyethyl isocyanate, 1,1-bis ((meth) acryloxymethyl) ethyl isocyanate, and the like.

These compounds can be used alone or in combination of two or more.

The polyfunctional isocyanate compound is not particularly limited, and examples thereof include the difunctional isocyanate compound; the uretdione dimer, isocyanurate trimer, and condensation of the difunctional isocyanate compound. Multimers such as diurea-type trimers. Furthermore, the two or three kinds of difunctional isocyanate compounds constituting the polymer may be the same or different.

These compounds can be used alone or in combination of two or more.

The polyfunctional alcohol compound is not particularly limited, and examples thereof include the difunctional alcohol compound; trimethylolpropane, pentaerythritol, di-trimethylolpropane, dipentaerythritol, and tris (2-hydroxyethyl). ) Tri- or higher-functional alcohol compounds such as isocyanurates, which are obtained by ring-opening addition of at least one selected from the cyclic ether compounds with these caprolactones Modified body; an alcohol compound obtained by ring-opening addition of a trifunctional or higher phenol compound such as phenol novolac and cresol novolac with at least one selected from the cyclic ether compounds. Lactone modification.

These compounds can be used alone or in combination of two or more.

From the viewpoints of heat resistance and solubility in an alkaline developer, the hardened (meth) acrylate having a urethane bond may further contain a carboxyl group if necessary.

The (meth) acrylic acid ester having a carboxyl group and a urethane bond is not particularly limited, and examples thereof include: when synthesizing the (meth) acrylic acid urethane, An alcohol compound is used in combination with the diol compound, or instead of the two (Meth) acrylic acid urethane obtained by using a carboxyl group-containing diol compound as an alcohol compound.

The carboxyl group-containing diol compound is not particularly limited, and examples thereof include 2,2-dimethylolbutanoic acid, 2,2-dimethylolpropionic acid, and 2,2-dimethylolvaleric acid. .

These compounds can be used alone or in combination of two or more.

The hardened (meth) acrylate having a carboxyl group and a urethane bond can be specified with an acid value in such a manner that it can be developed with an alkaline developing solution described later. The acid value is preferably 5 mgKOH / g to 200 mgKOH / g, more preferably 10 mgKOH / g to 170 mgKOH / g, and particularly preferably 15 mgKOH / g to 150 mgKOH / g.

When it is 5 mgKOH / g or more, the solubility in an alkaline developer is good, and when it is 200 mgKOH / g or less, the developer resistance is good.

In the curable resin composition for forming an optical waveguide, it is preferable to further use a polyfunctional blocked isocyanate compound as the (F) component. (F) A component reacts with the component which has a hydroxyl group and / or a carboxyl group, and produces a crosslinked structure. In this case, the component (B) is preferably a vinyl compound having a hydroxyl group or a carboxyl group. When the component (B) is not contained, it is desirable to formulate the compound (E) having a hydroxyl group or a carboxyl group that causes the reaction.

The polyfunctional blocked isocyanate compound as the component (F) is a compound produced by a reaction between a polyfunctional isocyanate compound and a blocking agent. In addition, it is a compound that is temporarily inactivated by a group derived from a blocking agent, and when heated to a predetermined temperature, the group derived from the blocking agent is dissociated to generate an isocyanate group. If a polyfunctional blocked isocyanate compound is used, the polyfunctional blocked isocyanate is heated from the polyfunctional blocked isocyanate compound. The isocyanate group formed in the compound reacts with the hydroxyl group and / or carboxyl group of the component (A), thereby forming a new crosslinked structure, and improving heat resistance and environmental reliability.

The polyfunctional isocyanate compound that can react with a blocking agent is not particularly limited, and examples thereof include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4- Aromatic polyfunctional isocyanate compounds such as toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, ortho-xylyl diisocyanate, meta-xylylene diisocyanate, etc. Acid methyl) cyclohexane, isophorone diisocyanate, 2,5-bis (isocyanatomethyl) norbornene, bis (4-isocyanatocyclohexyl) methane, 1,2- Bis (4-isocyanatocyclohexyl) ethane, 2,2-bis (4-isocyanatocyclohexyl) propane, 2,2-bis (4-isocyanatocyclohexyl) hexafluoropropane, Alicyclic polyfunctional isocyanate compounds such as dicycloheptane triisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate Aliphatic polyfunctional isocyanate compounds such as isocyanate and dodecylene diisocyanate.

The polyfunctional isocyanate compound is preferably a compound containing at least one selected from the group consisting of an alicyclic structure and an aliphatic structure from the viewpoint of transparency and heat resistance. Among them, the alicyclic formula is preferable. Polyfunctional isocyanate compound; the aliphatic polyfunctional isocyanate compound.

Furthermore, the polyfunctional isocyanate compound may be a multimer such as a uretdione dimer, an isocyanurate trimer, or a biuret trimer, and the two constituting the multimers The one or three kinds of polyfunctional isocyanate compounds may be the same or different. In addition, in different cases, for example, alicyclic polyfunctional isocyanate compounds and fats can be used. The combination of the family of polyfunctional isocyanate compounds is generally a combination of different kinds of polyfunctional isocyanate compounds.

The above polyfunctional isocyanate compounds may be used alone or in combination of two or more.

As the blocking agent, those having active hydrogen are preferred, and examples include malonic acid diester, acetic acid acetate, malonic acid dinitrile, acetic acid acetone, methylene difluorene, and dibenzoylmethane. , Methylene trimethylacetamethane, acetone dicarboxylic acid diester and other active methylene compounds; acetone oxime, methyl ethyl ketoxime, diethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone Oxime compounds such as oxime; phenol compounds such as phenol, alkylphenol, alkylnaphthol; γ-butyrolactam, δ-valprolactam, ε-caprolactam, and other lactam compounds.

Among these, from the viewpoints of transparency and heat resistance, the active methylene compound; the oxime compound; and the lactam compound are preferred.

The above blocking agents can be used alone or in combination of two or more.

In the curable resin composition of the present invention, the radical polymerization initiator used as the component (C) is subjected to heating or irradiation with actinic rays such as ultraviolet rays and visible rays, so that the components (A) and (B) are The free radical polymerization begins.

The radical polymerization initiator is not particularly limited as long as it is a radical polymerization initiator by heating or irradiation with actinic rays such as ultraviolet rays and visible rays. Examples include a thermal radical polymerization initiator, Photo radical polymerization initiators and the like.

The thermal radical polymerization initiator is not particularly limited, and examples thereof include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl cyclohexanone peroxide; 1, 1-bis (third butyl peroxide) cyclohexane, 1,1-bis (peroxide Tertiary butyl) -2-methylcyclohexane, 1,1-bis (third butyl peroxide) -3,3,5-trimethylcyclohexane, 1,1-bis (peroxide Trihexyl) cyclohexane, 1,1-bis (third hexyl peroxide) -3,3,5-trimethylcyclohexane and other peroxyketals; hydroperoxides such as mentane hydroperoxide ; Di, such as α, α'-bis (third butyl peroxide) dicumylbenzene, dicumyl peroxide, third butyl cumyl peroxide, di-third butyl peroxide Diperoxides such as octyl peroxide, lauryl peroxide, stearyl peroxide, benzamyl peroxide, etc .; bis (4-tert-butyl diperoxide) Cyclohexyl) ester, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxycarbonate, etc. ; Tributyl peroxy trimethylacetate, trihexyl peroxy trimethylacetate, 2-ethylhexanoic acid 1,1,3,3-tetramethylbutyl peroxide, 2,5- Dimethyl-2,5-bis (2-ethylhexyl peroxide) hexane, 2-ethylhexanoic acid tert-hexyl ester, 2-ethylhexanoic acid tert-butyl ester Tert-butyl peroxyisobutyrate, tert-hexyl isopropyl monocarbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl perlaurate, Isopropyl peroxy monobutyl carbonate, third ethyl butyl peroxy-2-ethylhexyl monocarbonate, third butyl peroxybenzoate, third hexyl peroxybenzoate, 2,5-di Peroxyesters such as methyl-2,5-bis (benzylidene peroxide) hexane, tert-butyl peracetate; 2,2'-azobisisobutyronitrile, 2,2'-azo Azo compounds such as bis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2'-dimethylvaleronitrile).

Among these, from the viewpoint of hardenability, transparency, and heat resistance, difluorenyl peroxide, peroxyester, and azo compound are preferred.

As a photoradical polymerization initiator, as long as it is through ultraviolet, visible light There are no particular restrictions on the start of radical polymerization by irradiation with actinic rays such as rays, and examples include benzoin such as 2,2-dimethoxy-1,2-diphenylethane-1-one Ketones; 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy 2-methyl-1-propane-1-one, 2-hydroxy-1- {4 [4- (2-hydroxy-2-methylpropanyl) benzyl] phenyl} -2-methylpropane Α-hydroxy ketones such as 1-one; methyl phenylglyoxylate, ethyl phenylglyoxylate, 2- (2-hydroxyethoxy) ethyl oxyphenylacetate, oxyphenylacetic acid 2 Glyoxylates such as 2- (2-oxo-2-phenylethoxyethoxy) ethyl ester; 2-benzyl-2-dimethylamino-1- (4-morpholine-4 -Ylphenyl) -butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-ylphenyl) -butane- Α-amino ketones such as 1-ketone, 1,2-methyl-1- [4- (methylthio) phenyl]-(4-morpholin) -2-ylpropane-1-one; 1,2 -Octanedione, 1- [4- (phenylthio), 2- (O-benzylideneoxime)], ethyl ketone, 1- [9-ethyl-6- (2-methylbenzidine ) -9H-carbazol-3-yl], 1- (O-acetamidooxime) and other oxime esters; bis (2,4,6-trimethylbenzyl) phenyl oxidation Bis (2,6-dimethoxybenzylidene) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, etc. Phosphine oxide; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxy Phenyl) -4,5-diphenylimidazole dimer and other 2,4,5-triarylimidazole dimers; benzophenone, N, N'-tetramethyl-4,4'-di Diphenyls such as aminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone Ketone compounds; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-benzene Anthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10- Quinone compounds such as phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; benzoin, methyl Benzoin compounds such as benzoin, ethyl benzoin; benzyl compounds such as benzyldimethylketal; acridine compounds such as 9-phenylacridine, 1,7-bis (9,9'-acridylheptane); N-phenylglycine, coumarin, and the like.

Here, the substituents of the aryl groups at the two triarylimidazole sites of the 2,4,5-triarylimidazole dimer may be the same to provide a symmetrical compound, or they may be different to provide an asymmetric compound.

Among the photo-radical polymerization initiators, from the viewpoints of hardenability and transparency, the α-hydroxy ketone, glyoxylate, oxime ester, or phosphine oxide described above is preferred.

The above-mentioned radical polymerization initiators (such as a thermal radical polymerization initiator and a photoradical polymerization initiator) can be used alone or in combination of two or more kinds, and can also be used in combination with an appropriate sensitizer.

In the curable resin composition of the present invention, the blending amounts of the (A) component, (B) component, and (C) component are (A) component is 5 wt% to 94.9 wt%, and (B) component is 5.0 wt% ~ 85wt%, and (C) component is 0.1wt% ~ 10wt%. (A) component is preferably 30% to 94.9% by weight, (B) component is 5.0% to 60% by weight, and (C) component is 0.1% to 10% by weight, and more preferably (A) is 40% by weight ~ 80wt%, (B) ingredient is 10wt% ~ 50wt%, and (C) ingredient is 1wt% ~ 5wt%.

In the curable resin composition of the present invention, a solvent and other additives may be blended as necessary. In the calculation of the blending amount in the curable resin composition, Volatile components such as solvents removed after curing are excluded from calculations.

When blending additives, the blending amounts of the (A) component, (B) component, and (C) component are relative to the total of (A) component, (B) component, and (C) component, and (A) component is 5 wt% to 94.9 wt%, (B) component is 5.0 wt% to 85 wt%, and (C) component is 0.1 wt% to 10 wt%. (A) component is preferably 30% to 94.9% by weight, (B) component is 5.0% to 60% by weight, and (C) component is 0.1% to 10% by weight, and more preferably (A) is 40% by weight ~ 80wt%, (B) ingredient is 10wt% ~ 50wt%, and (C) ingredient is 1wt% ~ 5wt%.

In addition, in the curable resin composition for forming the optical waveguide of the present invention, the blending amount of the (A) component, (B) component, and (C) component is 10% to 70% by weight of the (A) component, ( B) The component is 15 wt% to 70 wt%, and the (C) component is preferably 0.1 wt% to 10 wt%. Furthermore, it is desirable to formulate a polyfunctional blocked isocyanate compound as the (F) component and a compound having a hydroxyl group or a carboxyl group as the (E) component. The compounding amount of these compounds is 10% to 40% by weight of the (F) component. (E) The component is 0 wt% to 40 wt%. Here, the component (B) is preferably the component (B1), and further preferably the component (B) contains 10% to 70% by weight of a vinyl group (B2) having a hydroxyl group or a carboxyl group. When the (E) component is a vinyl compound having a hydroxyl group or a carboxyl group, calculation is performed as a component equivalent to both the (B) component and the (E) component.

From another viewpoint, when the component (E) is not included, the blending amount of the component (F) is preferably 1% to 40% by mass relative to the total amount of the components (A) to (C). In addition, when the component (E) is contained, the blending amount of the component (F) is preferably 1% to 40% by mass relative to the total amount of the components (A) to (C) and (E). the amount%. When the compounding amount of the (F) component is within the above range, a hydroxyl group and / or a carboxyl group of the (E) component reacts with an isocyanate group formed from a polyfunctional blocked isocyanate compound to form a sufficient crosslinked structure, so that it can be obtained. A hardened product that has good heat resistance, good toughness, and does not become brittle. From the above viewpoints, the blending amount of the (F) component is more preferably 3% by mass to 35% by mass, and particularly preferably 5% by mass to 30% by mass.

In the case of a curable resin composition for forming an optical waveguide, when the (meth) acrylate (B1) having a urethane bond is used as the component (B), the resin having an amino group can be used. The (meth) acrylic acid ester (B1) having an acid ester linkage is the entirety of the (B) component, but other vinyl compounds may be used if necessary.

In the resin composition of the present invention or the resin composition for forming a light waveguide, if necessary, an antioxidant, an anti-yellowing agent, an ultraviolet absorber, and visible light absorption can be added in a proportion that does not adversely affect the effects of the present invention. Agents, colorants, plasticizers, stabilizers, fillers, and so-called additives.

In addition, these resin compositions may be diluted with an appropriate organic solvent and used as a resin varnish. The organic solvent used here is not particularly limited as long as it dissolves the resin composition, and examples thereof include toluene, xylene, 1,3,5-trimethylbenzene, cumene, and p-isopropyltoluene. Aromatic hydrocarbons; chain ethers such as diethyl ether, third butyl methyl ether, cyclopentyl methyl ether, dibutyl ether; cyclic ethers such as tetrahydrofuran, 1,4-dioxane; methanol, ethanol, isopropyl ether Alcohols such as propanol, butanol, ethylene glycol, and propylene glycol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and other ketones; acetic acid Esters such as methyl ester, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone; carbonates such as ethyl carbonate, propylene carbonate; etc. Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethyl ether Difunctional alcohol alkyl ethers such as glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether Difunctional alcohol alkyl ether acetates such as propyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; N , N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and other amidines.

These organic solvents can be used alone or in combination of two or more. The solid content concentration in the resin varnish is usually preferably from 10% by mass to 80% by mass.

When the resin composition of the present invention or the resin composition for forming a waveguide is made into a varnish, it is preferably mixed by stirring. The stirring method is not particularly limited, but from the viewpoint of stirring efficiency, stirring using a propeller is preferred. The rotation speed of the propeller during stirring is not particularly limited, but it is preferably 10 rpm to 1,000 rpm. When the rotation speed of the propeller is 10 rpm or more, the components are sufficiently mixed, and if it is 1,000 rpm or less, the entrainment of air bubbles generated by the rotation of the propeller is reduced. From the above viewpoint, the rotation speed of the propeller is more preferably 50 rpm to 800 rpm, and particularly preferably 100 rpm to 500 rpm.

The stirring time is not particularly limited, but it is preferably from 1 hour to 24 hours. When the stirring time is 1 hour or more, the components are sufficiently mixed, and when it is 24 hours or less, the mixing time can be shortened and the productivity can be improved.

The varnish is preferably filtered using a filter having a pore size of 50 μm or less. By using a filter having a pore size of 50 μm or less, large foreign matter and the like are removed, and no dents or the like are generated during coating. In addition, light scattering is suppressed and transparency is not impaired. From the above viewpoint, it is more preferable to perform filtration using a filter having a pore size of 30 μm or less, and it is particularly preferable to perform filtration using a filter having a pore size of 10 μm or less.

In addition, when it is a resin varnish or a resin composition which is not a varnish and contains a volatile component, it is preferable to perform defoaming under reduced pressure. The defoaming method is not particularly limited, and examples thereof include a method using a vacuum pump, a bell jar, and a defoaming device with a vacuum device. The pressure during the reduced pressure is not particularly limited, but is preferably a pressure at which the low-boiling point component contained in the resin composition does not boil. The degassing time under reduced pressure is not particularly limited, but is preferably 3 minutes to 60 minutes. If the degassing time under reduced pressure is 3 minutes or more, bubbles dissolved in the resin composition can be removed, and if it is 60 minutes or less, the organic solvent contained in the resin composition will not volatilize and the defoaming time can be shortened. It can increase productivity.

Next, a resin film for forming a light guide tube of the present invention will be described.

This resin film is formed using the resin composition for forming the said optical waveguide. For example, it can be easily manufactured by applying a resin composition for forming a waveguide to an appropriate supporting film. In addition, when the resin composition is a resin varnish diluted with an organic solvent, it can be produced by coating the resin varnish on a support film and removing the organic solvent.

The supporting film is not particularly limited, and examples thereof include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polyolefins such as ethylene and polypropylene; polycarbonate, polyamidine, polyimide, polyamidide, imide, polyetherimide, polyether sulfide, polyether, polyetherketone, polyphenylene ether , Polyphenylene sulfide, polyarylate, polyfluorene, liquid crystal polymer, etc.

Among these, from the viewpoint of flexibility and toughness, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, and polycarbonate are preferred. Esters, polyamidoamines, polyamidoimines, polyamidoimines, polyphenylene ethers, polyphenylene sulfide, polyarylates, polyamidoamines.

In addition, from the viewpoint of improving the releasability from the resin layer, a film subjected to a release treatment with a silicone-based compound, a fluorine-containing compound, or the like may be used as necessary.

The thickness of the support film can be appropriately changed depending on the target flexibility, but from the viewpoint of film strength and flexibility, it is preferably 3 μm to 250 μm, more preferably 5 μm to 200 μm, and particularly preferably 7 μm to 150 μm.

A film formed by coating a resin composition for forming a light guide tube on a support film may have a protective film attached to the resin layer, if necessary, to form a three-layer structure including a support film, a resin layer, and a protective film.

The protective film is not particularly limited, but in terms of flexibility and toughness, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like are preferred. Polyester; Polyolefins such as polyethylene and polypropylene. In addition, from the viewpoint of improving the releasability from the resin layer, a film subjected to a release treatment with a silicone-based compound, a fluorine-containing compound, or the like may be used as necessary.

The thickness of the protective film is preferably 10 μm to 250 μm, more preferably 15 μm to 200 μm, and particularly preferably 20 μm to 150 μm.

The thickness of the resin layer of the resin film for forming a light waveguide of the present invention is not particularly limited, but it is usually preferably 5 μm to 500 μm in terms of the thickness after drying. Within this range, the strength of the resin film or the cured product of the resin film is sufficient, and the drying can be sufficiently performed at the same time. Therefore, the amount of the residual solvent in the resin film does not increase. Will foam.

The resin film for forming a light-guide tube obtained as described above can be easily stored by being rolled into a roll shape, for example. In addition, the roll-shaped film may be cut into a desired size, and stored in a sheet shape.

Next, an application example when the resin film for forming a light guide tube of the present invention is used as a resin film for forming a core portion will be described.

The supporting film in this case is not particularly limited as long as it is a transmissive actinic ray for the formation of a core pattern. For example, a supporting film that is a supporting film that is the resin film for forming a light guide tube may be appropriately listed. The same support film described in the specific example.

Among these, polyesters and polyolefins are preferred from the viewpoints of transmittance, flexibility, and toughness of actinic rays for exposure. Furthermore, from the viewpoint of improving the transmittance of actinic rays for exposure and reducing the side wall roughness of the core pattern, it is more preferable to use a highly transparent support film. As such a highly transparent support film, among the marketers, for example, "Cosmoshine A1517" and "Cosmoshine A4100" manufactured by Toyobo Co., Ltd., and "Lumirror" manufactured by Toray Co., Ltd. FB50 "and so on.

From the standpoint of strength and pattern resolution at the time of core pattern formation, this branch The thickness of the supporting film is preferably 5 μm to 50 μm, more preferably 10 μm to 40 μm, and particularly preferably 15 μm to 30 μm.

Next, a case where the resin film for forming a light guide tube of the present invention is used as a resin film for forming a cladding (a resin film for forming an upper cladding layer and a resin film for forming a lower cladding layer) will be described.

The supporting film in this case is not particularly limited as long as it is a transmissive actinic ray for exposure for cladding formation, and for example, a supporting film that is a supporting film that is the resin film for forming a light guide tube may be appropriately listed. The same support film described in the specific example.

Among these, polyesters and polyolefins are preferred from the viewpoints of transmittance, flexibility, and toughness of actinic rays for exposure. Furthermore, from the viewpoint of increasing the transmittance of actinic rays for exposure and reducing the roughness of the sidewall of the cladding pattern, it is more preferable to use a highly transparent support film. As such a highly transparent support film, among the marketers, for example, "Cosmoshine A1517" and "Cosmoshine A4100" manufactured by Toyobo Co., Ltd., and "Lumirror" manufactured by Toray Co., Ltd. FB50 "and so on.

The thickness of the support film of the resin film for cladding formation is preferably 5 μm to 50 μm, more preferably 10 μm to 40 μm, and particularly preferably 15 μm to 30 μm.

Next, the optical waveguide of the present invention will be described.

1 (a) to 1 (d) are cross-sectional views of a light guide tube, respectively.

In FIG. 1 (a), a light waveguide 1 is formed on a substrate 5 and includes a core portion 2 including a resin composition for core formation with a high refractive index, and a resin composition for a cladding formation including a low refractive index.的 下 clad 4 and upper cladding 3.

1 (b) to 1 (d) show other modes, respectively. FIG. 1 (b) shows a state in which a base material 5 is disposed as a protective film on the outside of the upper cladding layer 3. FIG. 1 (c) shows a state in which a base material 5 is disposed as a protective film on the outside of both the lower cladding layer 4 and the upper cladding layer 3. As shown in FIG. 1 (d), the aspect of the base material as the protective film 5 is not shown.

The resin composition for forming a light guide tube and the resin film for forming a light waveguide of the present invention are preferably used for at least one of the lower cladding 4, the core 2, and the upper cladding 3 of the light waveguide 1, It is preferable to use those whose refractive indices are adjusted for all layers.

By using the resin film for optical waveguide formation, the flatness of each layer, the interlayer adhesion between the cladding and the core, and the resolution (correspondence of thin lines or narrow gaps) when the optical waveguide die pattern is formed can be further improved. Fine pattern with excellent flatness and small line width or gap.

The material of the substrate 5 in the optical waveguide 1 is not particularly limited, and examples thereof include glass epoxy substrates, ceramic substrates, glass substrates, silicon substrates, plastic substrates, metal substrates, and substrates with resin layers. , Substrate with metal layer, plastic film, plastic film with resin layer, plastic film with metal layer, etc.

The optical waveguide 1 can be made into a flexible optical waveguide by using a substrate having flexibility and toughness as the substrate 5 such as a support film of the resin film for forming the optical waveguide as the substrate. In this case, the base material 5 can also be made to function as a protective film of the optical waveguide 1. By disposing the protective film, the flexibility and toughness of the protective film can be imparted to the optical waveguide 1. Furthermore, the optical waveguide 1 is not contaminated or damaged, so Ease of improvement.

From the viewpoints described above, the form shown in Figs. 1 (b) to 1 (c) may be suitable instead of the form shown in Fig. 1 (a). If the flexibility or toughness of the optical waveguide is sufficient, as shown in FIG. 1 (d), the protective film may be omitted.

The thickness of the lower cladding layer 4 is not particularly limited, but is preferably 2 μm to 200 μm. If it is 2 μm or more, it is easy to seal the propagating light inside the core, and if it is 200 μm or less, the thickness of the entire optical waveguide tube 1 is not excessively large. The thickness of the lower cladding layer 4 is a value from the boundary between the core portion 2 and the lower cladding layer 4 to the lower surface of the lower cladding layer 4.

The thickness of the resin film for forming a lower cladding layer is not particularly limited, and the thickness is adjusted so that the thickness of the lower cladding layer 4 after curing becomes the above range.

The height of the core portion 2 is not particularly limited, but is preferably 10 μm to 150 μm. If the height of the core is 10 μm or more, the alignment tolerance will not be reduced in the combination with the optical transceiver element or optical fiber after the optical waveguide is formed. If it is 150 μm or less, the optical waveguide after the optical waveguide is formed In the combination of transmitting and receiving elements or optical fibers, the bonding efficiency does not decrease. From the above viewpoints, the height of the core is more preferably 15 μm to 130 μm, and particularly preferably 20 μm to 120 μm. The thickness of the resin film for forming a core is not particularly limited, and the thickness is adjusted so that the height of the core after curing becomes the above range.

The thickness of the upper cladding layer 3 is not particularly limited as long as it is a range in which it can be embedded in the core portion 2, but it is preferably 12 μm to 500 μm in terms of the thickness after drying. The thickness of the upper cladding layer 3 may be the same as the thickness of the lower cladding layer 4 that is initially formed. It may be different, but it is preferably thicker than the lower cladding layer 4 from the viewpoint of embedding the core portion 2. The thickness of the upper cladding layer 3 is a value from the boundary between the core portion 2 and the lower cladding layer 4 to the upper surface of the upper cladding layer 3.

In the optical waveguide of the present invention, the light propagation loss in a light source with a wavelength of 850 nm is preferably 0.3 dB / cm or less, more preferably 0.2 dB / cm or less, and particularly preferably 0.1 dB / cm or less.

In addition, the light transmission loss in a light source with a wavelength of 850 nm after a high-temperature and high-humidity storage test at a temperature of 85 ° C and a humidity of 85% for 1,000 hours is preferably 0.3 dB / cm or less, more preferably 0.2 dB / cm or less, and particularly preferably 0.1dB / cm or less.

The high-temperature and high-humidity placement test refers to a high-temperature and high-humidity placement test performed under conditions of the Japan Electronics Packaging Circuits Association (JPCA) specification (JPCA-PE02-05-01S).

Furthermore, the light propagation loss in a light source with a wavelength of 850 nm after performing a temperature cycle test between -55 ° C and 125 ° C is preferably 0.3 dB / cm or less, more preferably 0.2 dB / cm or less, and particularly preferably 0.1dB / cm or less.

It should be noted that the temperature cycle test refers to a temperature cycle test performed under conditions according to the JPCA standard (JPCAPE02-05-01S).

In addition, the light propagation loss in a light source with a wavelength of 850 nm after performing a reflow test at a maximum temperature of 265 ° C three times is preferably 0.3 dB / cm or less, more preferably 0.2 dB / cm or less, and particularly preferably 0.1 dB / cm or less. .

Furthermore, the reflow test is based on the specifications of the Joint Electron Device Engineering Council (JEDEC) (JEDEC JESD22A113E).

The optical waveguide of the present invention is excellent in transparency, environmental reliability, and heat resistance, and can be used as an optical transmission tube of an optical module. Examples of the form of the optical module include an optical waveguide tube with an optical fiber formed by connecting an optical fiber to both ends of the optical waveguide tube, and a connector with a connector formed by connecting the connector to both ends of the optical waveguide tube. Optical waveguide tube, a photoelectric composite substrate obtained by compounding a light waveguide tube and a printed wiring board, a photoelectric conversion module combining a light waveguide tube and an optical / electric conversion element that converts optical signals and electrical signals into each other, A wavelength multiplexer / demultiplexer, etc., which is a combination of an optical waveguide tube and a wavelength division filter.

In addition, the photovoltaic composite substrate is not particularly limited as a composite printed wiring board, and examples thereof include rigid substrates such as glass epoxy substrates and ceramic substrates; polyimide substrates and polyethylene terephthalate. Flexible substrates such as diester substrates.

Hereinafter, a manufacturing method for forming a light waveguide using the resin composition for forming a light waveguide or the resin film for forming a light waveguide according to the present invention will be described.

The method for manufacturing the optical waveguide is not particularly limited, and examples thereof include a method for manufacturing the optical waveguide tube forming resin layer on the substrate using the resin composition or film.

The method for forming the resin layer for forming a light waveguide is not particularly limited, and examples thereof include the use of a resin composition for forming a light waveguide, a spin coating method, a dip coating method, a spray method, a rod coating method, and a roll coating method. Methods such as coating, curtain coating, gravure coating, screen coating, inkjet coating, and the like.

When the resin composition for optical waveguide tube formation is diluted with the organic solvent to become a resin varnish for optical waveguide tube formation, a step of drying may be added after the resin layer is formed, if necessary. The drying method is not particularly limited, and examples thereof include heating and drying under reduced pressure. If necessary, these may be used in combination.

As another method of forming the resin layer for forming a light waveguide, a method of forming the resin layer for forming a light waveguide by a lamination method may be used.

Among these, from the viewpoint of forming a light guide tube having excellent flatness and having a fine pattern with a small line width or gap, it is preferable to use a lamination method to manufacture the light guide tube using a resin film for forming a light guide tube. method.

Next, a manufacturing method for forming the light guide tube 1 by using the resin film for forming a light guide tube for the lower cladding layer, the core portion, and the upper cladding layer will be described, but the present invention is not limited at all by the manufacturing method.

First, as a first step, a resin film for forming a lower cladding layer is laminated on the base material 5. The lamination method in the first step is not particularly limited, and examples thereof include a method of laminating using a roll laminator or a flat-bed laminator while pressing and heating while heating. In addition, the flat-bed laminator in the present invention refers to a laminator that sandwiches a laminated material between a pair of flat plates and presses the flat plates. For example, a vacuum press type can be suitably used. Laminator. The lamination temperature is not particularly limited, but is preferably 20 ° C to 130 ° C, and the lamination pressure is not particularly limited, but is preferably 0.1 MPa to 1.0 MPa. When a protective film is present in the resin film for forming a lower cladding layer, lamination is performed after removing the protective film.

When laminating using a vacuum press laminator, roll lamination can be used Machine, the lower cladding layer forming resin film is temporarily attached to the substrate 5 in advance. Here, from the viewpoint of improving the adhesiveness and followability, it is preferable to perform temporary bonding while pressing and bonding, and when performing the pressing, a laminator having a heat roller can be used while pressing while heating. Pick up. The lamination temperature is preferably 20 ° C to 150 ° C, and more preferably 40 ° C to 130 ° C. If it is this range, the adhesiveness of a resin film and a base material will improve, and a resin layer will not flow excessively at the time of roll lamination, and a desired film thickness can be obtained. The lamination pressure is not particularly limited, but is preferably 0.2 MPa to 0.9 MPa, and the lamination speed is not particularly limited, but is preferably 0.1 m / min to 3 m / min.

The lower cladding layer forming resin layer laminated on the base material 5 is hardened by light and / or heat to form the lower cladding layer 4. The removal of the support film of the resin film for forming a lower cladding layer may be performed at any time before and after curing.

The irradiation amount of actinic rays when the resin layer for forming a lower cladding layer is hardened by light is not particularly limited, but it is preferably set to 0.1 J / cm ² to 5 J / cm ² . In addition, when the actinic rays are transmitted through the substrate, in order to effectively harden, a double-sided exposure machine capable of simultaneously irradiating actinic rays from both sides can be used. In addition, actinic rays may be irradiated while heating. Moreover, as a process before and after photo-hardening, you may heat-process 50 to 200 degreeC as needed.

The heating temperature when the resin layer for forming a lower cladding layer is hardened by heat is not particularly limited, but it is preferably set to 50 ° C to 200 ° C.

When the support film of the resin film for lower cladding formation is made to function as the protective film 5 of the light waveguide 1, the resin film for lower cladding formation may not be laminated, and the light and / or heat may be used under the same conditions as described above. Hardened to form the lower cladding layer 4.

In addition, the protective film of the resin film for forming a lower cladding layer may be removed before curing or may be removed after curing.

As a second step, a resin film for core formation was laminated on the lower cladding layer 4 in the same manner as in the first step. Here, it is preferable that the resin layer for forming a core part is designed to have a refractive index higher than that of the resin layer for forming a lower cladding layer, and contains a photosensitive resin capable of forming the core part 2 (core pattern) by actinic rays. Thing.

As a third step, the core portion 2 is exposed. The method for exposing the core 2 is not particularly limited, and examples thereof include a method of irradiating actinic rays in an image shape through a negative mask called an artwork, and not transmitting negative light. A method of directly irradiating an actinic ray on an image using a laser, etc. using a mask.

The source of actinic rays is not particularly limited, and examples thereof include ultrahigh-pressure mercury lamps, high-pressure mercury lamps, mercury vapor arc lamps, metal halide lamps, xenon lamps, and carbon arc lamps, which effectively emit ultraviolet light; Light sources such as light lamps and fluorescent lamps that effectively emit visible light.

The irradiation dose of actinic rays when the core 2 is exposed is preferably 0.01 J / cm ² to 10 J / cm ² , more preferably 0.03 J / cm ² to 5 J / cm ² , and even more preferably 0.05 J / cm. ² ~ 3J / cm ² . If it is this range, a hardening reaction will fully advance and a core part will not lose | release by development, On the other hand, a core part does not become thick due to an excessive exposure amount, and it is suitable to form a fine pattern. The exposure of the core part 2 may be performed through the support film of the resin film for core formation, or may be performed after removing a support film.

In addition, from the viewpoint of improving the resolution and adhesion of the core 2 after exposure, In other words, post-exposure heating may be performed as necessary. The time from ultraviolet irradiation to heating after exposure is preferably within 10 minutes, but this condition is not particularly limited. The heating temperature after exposure is preferably 40 ° C to 160 ° C, and the time is preferably 30 seconds to 10 minutes, but these conditions are not particularly limited.

As a 4th step, when exposing through the support film of the resin film for core formation, this support film is removed, and it develops using a developing solution.

The development method is not particularly limited, and examples thereof include a spray method, a dipping method, a liquid coating method, a rotation method, a brushing method, and a scraping method. These development methods may be used in combination as necessary. The developing solution is not particularly limited, and examples thereof include organic solvents, quasi-aqueous developing solutions containing organic solvents and water, aqueous-based alkaline developing solutions containing alkaline aqueous solutions, and quasi-aqueous alkaline solutions containing alkaline aqueous solutions and organic solvents. Developer and so on. The developing temperature is adjusted in accordance with the developability of the resin layer for core formation.

The organic solvent is not particularly limited, and for example, the same as the organic solvent used for diluting the resin composition for forming a light-guide tube may be suitably used. These compounds can be used alone or in combination of two or more. In addition, a surfactant, an antifoaming agent, or the like may be mixed into the organic solvent. The quasi-water-based developer is not particularly limited as long as it contains one or more organic solvents and water. The concentration of the organic solvent is preferably 5 to 90% by mass. In addition, a small amount of a surfactant, a defoamer, etc. may be mixed into the quasi-water-based developer.

The base of the alkaline aqueous solution is not particularly limited, and examples thereof include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; hydrogen carbonate Basic gold such as lithium, sodium bicarbonate, potassium bicarbonate It is a bicarbonate salt; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; sodium salts such as sodium tetraborate and sodium metasilicate; Salt; tetramethylammonium hydroxide, triethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2- Organic bases such as morpholine. These compounds can be used alone or in combination of two or more.

The pH of the aqueous alkaline developer is preferably 9 to 14. In addition, a surfactant, a defoamer, and the like may be mixed into the aqueous alkaline developing solution.

The quasi-water-based alkaline developer is not particularly limited as long as it contains an alkaline aqueous solution and one or more of the organic solvents. The organic solvent is not particularly limited, and examples thereof include the same ones as those used for diluting the resin composition for forming a light guide tube. It is preferable that the pH of the quasi-water-based alkaline developer is as small as possible within a range in which the development can be sufficiently performed, and the pH is preferably 8 to 13, more preferably the pH is 9 to 12. The concentration of the organic solvent is usually preferably 5 to 90% by mass. In addition, a small amount of a surfactant, a defoamer, etc. may be mixed into the quasi-water-based alkaline developer.

As a treatment after development, an organic solvent, a quasi-water-based cleaning solution, or water may be used for cleaning as necessary. The cleaning method is not particularly limited, and examples thereof include a spray method, a dipping method, a liquid coating method, a rotation method, a brushing method, and a scraping method. If necessary, these cleaning methods may be used in combination. The organic solvents may be used alone or in combination of two or more. The concentration of the organic solvent in the quasi-water-based cleaning solution is usually preferably set to 5 to 90% by mass. The cleaning temperature is adjusted in accordance with the developability of the resin layer for core formation.

As a treatment after development or cleaning, from the viewpoint of improving the hardenability and adhesion of the core portion 2, exposure and / or heating may be performed as necessary. The heating temperature is not particularly limited, but is preferably 40 ° C. to 200 ° C., and the irradiation amount of actinic rays is not particularly limited, but is preferably 0.01 J / cm ² to 10 J / cm ² .

As a fifth step, a resin film for forming an upper cladding layer was laminated on the lower cladding layer 4 and the core portion 2 in the same manner as in the first step and the second step. Here, the resin layer for forming an upper cladding layer is designed so that its refractive index is lower than that of the resin layer for forming a core portion. The thickness of the upper cladding layer-forming resin layer is preferably larger than the height of the core portion 2.

In the same manner as in the first step, the upper cladding layer forming resin layer is hardened by light and / or heat to form the upper cladding layer 3. The irradiation amount of actinic rays when the resin layer for forming the upper cladding layer is hardened by light is not particularly limited, but it is preferably set to 0.1 J / cm ² to 30 J / cm ² . In addition, when the actinic rays are transmitted through the substrate, in order to effectively harden, a double-sided exposure machine capable of simultaneously irradiating actinic rays from both sides can be used. In addition, actinic rays may be irradiated while heating as needed, and heat treatment may be performed as a treatment before and after photocuring. The heating temperature during actinic ray irradiation and / or after irradiation is not particularly limited, but is preferably 50 ° C to 200 ° C. The heating temperature when the resin layer for forming the upper cladding layer is hardened by heat is not particularly limited, but is preferably 50 ° C to 200 ° C.

Furthermore, when it is necessary to remove the support film of the resin film for forming the upper cladding layer, it may be removed before curing or after curing.

The above steps can be used to fabricate the optical waveguide 1.

[Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples. The parts in each example are all parts by weight, and the measurement of physical properties was performed by the method shown below.

1) Molecular weight and molecular weight distribution of the copolymer (soluble polyfunctional aromatic copolymer)

The molecular weight and molecular weight distribution were measured using a Gel Permeation Chromatograph (GPC) (manufactured by Tosoh, HLC-8120GPC). Tetrahydrofuran was used as a solvent at a flow rate of 1.0 ml / min and a column temperature of 38 ° C. This was done using a calibration curve for monodisperse polystyrene.

2) Structure of the copolymer

The JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by Japan Electronics was used, and determined by ¹³ C-nuclear magnetic resonance (NMR) and ¹ H-NMR analysis. Chloroform-d _{1 was} used as a solvent, and a resonance line of tetramethylsilane was used as an internal standard.

3) Analysis of terminal groups

The calculation of the terminal group is based on the number-average molecular weight obtained from the GPC measurement and the result from ¹ H-NMR measurement and gas chromatography (Gas Chromatograph, GC) analysis relative to the total monomer. The amount of a derivative for introducing a terminal group was calculated, and the number of terminal groups contained in one molecule of a soluble polyfunctional vinyl aromatic copolymer having a terminal group was calculated.

4) Measurement of the glass transition temperature (Tg) and softening temperature of the hardened material

Uniform the copolymer solution so that the thickness after drying becomes 20 μm It was apply | coated on the glass substrate, and it dried by heating at 90 degreeC for 30 minutes using the hotplate. The glass substrate and the obtained resin film were set on a thermomechanical analyzer (TMA) (thermomechanical analysis device), and the temperature was raised to 220 ° C at a temperature increase rate of 10 ° C / min under a nitrogen gas flow, and further The copolymer was hardened by performing a heat treatment at 220 ° C for 20 minutes to remove the residual solvent. After the glass substrate is left to cool to room temperature, the probe for analysis is brought into contact with the sample in the TMA measurement device, and scanning measurement is performed at a temperature rising rate of 10 ° C / min from 30 ° C to 360 ° C under a nitrogen gas flow, and The tangent method was used to determine the softening temperature.

Regarding the glass transition temperature, the test piece was set on a Dynamic Mechanical Analyzer (DMA) (Dynamic Viscoelastic Device) measuring device, and the temperature was increased from 30 ° C to 320 ° C at a temperature increase rate of 3 ° C / min under a stream of nitrogen. Scanning was performed until the temperature was reached, and Tg was obtained from the peak top of the tan δ curve.

5) Evaluation of heat resistance and measurement of heat discoloration resistance

The heat resistance of the copolymer was evaluated by setting the sample on a Thermal Gravimetric Analyzer (TGA) measuring device under a nitrogen gas flow at a temperature increase rate of 10 ° C / min from 30 ° C to 400 ° C. Scanning was performed until measurement was performed, and the weight loss at 350 ° C was determined as heat resistance. On the other hand, the measurement of heat discoloration resistance was performed by mixing 6.0 g of a copolymer, 4.0 g of benzyl methacrylate, and 0.02 g of tert-butyl peroxy-2-ethylhexanoate, and mixing at 200 ° C. under a nitrogen stream. It was heated for 1 hour, and the hardened | cured material was obtained. Then, the amount of discoloration of the obtained cured product was visually confirmed, and classified into ○: no thermal discoloration, △: light yellow, ×: yellow, and the resistance was performed. Evaluation of thermal discoloration.

6) Determination of compatibility

The compatibility of the copolymer and the epoxy resin was measured by using 5.0 g of a sample, 3.0 g of an epoxy resin (liquid bisphenol A type epoxy resin: manufactured by Japan Epoxy Resin Co., Epikote828), and phenol resin ( Melamine skeleton phenol resin: manufactured by Qunei Chemical Industry Co., Ltd. (PS-6492) 2.0 g was dissolved in 10 g of Methyl Ethyl Ketone (MEK), and the transparency of the dissolved sample was visually confirmed and classified ○: Transparent, △: Translucent, ×: Opaque or undissolved, and compatibility was evaluated.

Synthesis Example 1

Divinylbenzene (a mixture of 1,4-divinylbenzene and 1,3-divinylbenzene, the same applies to the following examples) 1.28 moles (182.7mL), ethyl vinylbenzene (1-ethyl Mixture of 4-vinylbenzene and 1-ethyl-3-vinylbenzene, the same applies to the following examples) 0.97 mole (137.8mL), third butyl methacrylate 2.00 mole (323.2mL), toluene 300 mL was put into a 2.0 L reactor, and 50 millimoles of diethyl ether complex of boron trifluoride was added at 50 ° C, and a reaction was performed for 4 hours. After the polymerization was stopped with an aqueous solution of sodium bicarbonate, the oil layer was washed three times with pure water, and evaporated under reduced pressure at 60 ° C. to recover the polymer. The obtained polymer was weighed, and it was confirmed that 234.6 g of copolymer A was obtained.

The Mn of the obtained copolymer A was 842, Mw was 3640, and Mw / Mn was 4.32. By ¹³ C-NMR and ¹ H-NMR analysis, the copolymer A observed a resonance line derived from the terminal group of the third butyl methacrylate. The introduction amount (c1) of the structural unit derived from the third butyl methacrylate of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis result and the number average molecular weight in terms of standard polystyrene was 2.3 (units / molecule). In addition, it contains 60.1 mol% of divinylbenzene-derived structural units and 39.9 mol% of ethylvinylbenzene-derived structural units (excluding terminal structural units) in total. The vinyl content contained in the copolymer A was 36.2 mol% (except for the terminal structural unit).

In addition, as a result of TMA measurement of the cured product, no clear Tg was observed, and the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight reduction at 350 ° C was 2.80 wt%, and the heat discoloration resistance was ○. On the other hand, compatibility with epoxy resin was ○.

Copolymer A was soluble in toluene, xylene, tetrahydrofuran (THF), dichloroethane, dichloromethane, and chloroform, and no gel formation was observed.

Synthesis Example 2

1.28 mol (182.7 mL) of divinylbenzene, 0.97 mol (137.8 mL) of ethyl vinyl benzene, 2.00 mol (289.6 mL) of third butyl acrylate, and 300 mL of toluene were put into a 2.0 L reactor. 50 millimoles of diethyl ether complex of boron trifluoride was added at 50 ° C, and a reaction was performed for 4 hours. After the polymerization was stopped with an aqueous solution of sodium bicarbonate, the oil layer was washed three times with pure water, and evaporated under reduced pressure at 60 ° C. to recover the polymer. The obtained polymer was weighed, and it was confirmed that 215.3 g of copolymer B was obtained.

The Mn of the obtained copolymer B was 952, Mw was 4,490, and Mw / Mn was 4.72. By ¹³ C-NMR and ¹ H-NMR analysis, the copolymer B observed a resonance line derived from the terminal group of the third butyl acrylate. The introduction amount (c1) of the structural unit derived from the third butyl acrylate in the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis result and the number average molecular weight in terms of standard polystyrene was 2.5 (units / molecule) . In addition, it contains 59.3 mol% of divinylbenzene-derived structural units and 40.7 mol% of ethylvinylbenzene-derived structural units (excluding terminal structural units) in total. The content of the vinyl group in the copolymer B was 34.7 mol% (excluding the terminal structural unit).

In addition, as a result of TMA measurement of the cured product, no clear Tg was observed, and the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C. was 3.04 wt%, and the heat discoloration resistance was ○. On the other hand, compatibility with epoxy resin was ○.

Copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed.

Synthesis example 3 (comparative example)

Divinylbenzene 2.03 moles (288.5mL), ethyl vinylbenzene 0.084 moles (12.0mL), styrene 2.11 moles (241.7mL), 2-phenoxyethyl methacrylate 2.25 moles ( 427.3 mL), 100.0 mL of butyl acetate, and 1150 mL of toluene were charged into a 3.0 L reactor, and 300 millimoles of diethyl ether complex of boron trifluoride was added at 50 ° C., and a reaction was performed for 4 hours. After the polymerization was stopped with an aqueous solution of sodium bicarbonate, the oil layer was washed three times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried, and weighed to obtain 282.4 g of copolymer C.

The Mn of the obtained copolymer C was 2030, Mw was 5180, and Mw / Mn was 2.55. By ¹³ C-NMR and ¹ H-NMR analysis, the copolymer C observed a resonance line derived from a terminal group of 2-phenoxyethyl methacrylate. As a result of elemental analysis of the copolymer C, C: 87.3% by weight, H: 7.4% by weight, and O: 5.2% by weight. The introduction amount (c1) of the structural unit derived from 2-phenoxyethyl methacrylate of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis result and the number average molecular weight in terms of standard polystyrene was 2.3 (Pcs / molecule). In addition, it contains 59.2 mol% of divinylbenzene-derived structural units and 40.8 mol% of styrene and ethylbenzene-derived structural units (excluding terminal structural units). The vinyl content contained in the copolymer C was 35.3 mol% (except for the terminal structural unit).

In addition, as a result of TMA measurement of the cured product, no clear Tg was observed, and the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C. was 4.86 wt%, and the heat discoloration resistance was ○. On the other hand, the compatibility with epoxy resin is △.

Copolymer C was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed.

Synthesis example 4 (comparative example)

Divinylbenzene 1.92 moles (273.5mL), ethyl vinylbenzene 0.08 moles (11.4mL), styrene 2.0 moles (229.2mL), 2-phenoxyethyl acrylate 2.00 moles (348.1mL) ), 250.0 mL of butyl acetate, and 1000 mL of toluene were put into a 3.0 L reactor, and 80 millimoles of diethyl ether complex of boron trifluoride was added at 70 ° C., and the reaction was performed for 6 hours. After the polymerization was stopped with an aqueous solution of sodium bicarbonate, the oil layer was washed three times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried, and weighed to obtain 164.2 g of a copolymer. D.

The Mn of the obtained copolymer D was 2330, Mw was 4940, and Mw / Mn was 2.12. By ¹³ C-NMR and ¹ H-NMR analysis, the copolymer D observed a resonance line derived from a terminal group of 2-phenoxyethyl acrylate. As a result of elemental analysis of the copolymer D, C: 84.4 wt%, H: 7.3 wt%, and O: 7.9 wt%. The introduction amount (c1) of the structural unit derived from 2-phenoxyethyl acrylate of the soluble polyfunctional vinyl aromatic polymer calculated based on the elemental analysis result and the number average molecular weight in terms of standard polystyrene was 3.5 (units) /molecule). In addition, it contains 54.3 mol% of structural units derived from divinylbenzene and a total of 45.7 mol% of structural units derived from styrene and ethylbenzene (excluding terminal structural units). The content of the vinyl group contained in the copolymer D was 21.8 mol% (excluding the terminal structural unit).

In addition, as a result of TMA measurement of the cured product, no clear Tg was observed, and the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C was 5.50 wt%, and the heat discoloration resistance was ○. On the other hand, the compatibility with epoxy resin is △.

Copolymer D was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed.

Synthesis Example 5

Divinylbenzene 1.024 moles (146.2mL), ethyl vinylbenzene 0.776 moles (110.2mL), styrene 0.45 moles (51.7mL), and tertiary butyl methacrylate 2.00 moles (323.2mL) 300 mL of toluene was put into a 2.0 L reactor, and 50 millimoles of diethyl ether complex of boron trifluoride was added at 50 ° C, and a reaction was performed for 4 hours. After stopping the polymerization with an aqueous solution of sodium bicarbonate, pure water was used. The oil layer was washed three times, and it was devolatilized under reduced pressure at 60 ° C, and the polymer was recovered. The obtained polymer was weighed, and it was confirmed that 225.7 g of copolymer E was obtained.

The Mn of the obtained copolymer E was 789, Mw was 3450, and Mw / Mn was 4.37. By ¹³ C-NMR and ¹ H-NMR analysis, the copolymer E observed a resonance line derived from the terminal group of the third butyl methacrylate. The introduction amount (c1) of the structural unit derived from the third butyl methacrylate of the soluble polyfunctional vinyl aromatic polymer calculated based on the elemental analysis result and the number average molecular weight in terms of standard polystyrene was 2.4 (units / molecule). In addition, it contains 47.1 mole% of structural units derived from divinylbenzene, 34.0 mole% of structural units derived from ethylvinylbenzene, and 18.9 mole% of structural units derived from styrene (terminal structure Except units). The content of the vinyl group contained in the copolymer E was 33.8 mol% (excluding the terminal structural unit).

In addition, as a result of TMA measurement of the cured product, no clear Tg was observed, and the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C. was 3.37 wt%, and the heat discoloration resistance was ○. On the other hand, compatibility with epoxy resin was ○.

Copolymer E was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed.

Synthesis Example 6

Divinylbenzene 1.024 moles (146.2mL), ethyl vinylbenzene 0.776 moles (110.2mL), divinyl biphenyl 0.45 moles (81.1g), and tertiary butyl methacrylate 2.00 moles ( 323.2 mL) and 300 mL of toluene were put into a 2.0 L reactor, and 50 millimoles of diethyl ether complex of boron trifluoride was added at 50 ° C., and a reaction was performed for 4 hours. After stopping the polymerization with an aqueous solution of sodium bicarbonate, use The oil layer was washed three times with pure water, devolatilized under reduced pressure at 60 ° C, and the polymer was recovered. The obtained polymer was weighed, and it was confirmed that 318.7 g of copolymer F was obtained.

The Mn of the obtained copolymer F was 913, Mw was 4210, and Mw / Mn was 4.61. By ¹³ C-NMR and ¹ H-NMR analysis, the copolymer F observed a resonance line derived from the terminal group of the third butyl methacrylate. The introduction amount (c1) of the structural unit derived from the third butyl methacrylate of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis result and the number average molecular weight in terms of standard polystyrene was 2.2 (units / molecule). In addition, it contains 47.3 mole% of structural units derived from divinylbenzene, 34.5 mole% of structural units derived from ethylvinylbenzene, and 18.2 mole% of structural units derived from styrene (terminal structure Except units). Copolymer F had a vinyl content of 32.9 mol% (except for the terminal structural unit).

In addition, as a result of TMA measurement of the cured product, no clear Tg was observed, and the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 350 ° C was 2.92 wt%, and the heat discoloration resistance was ○. On the other hand, compatibility with epoxy resin was ○.

Copolymer F was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed.

Using the copolymers A to F obtained in Synthesis Example 1 to Synthesis Example 6, the properties of the varnish and the cured product of the curable resin composition using these resins were evaluated according to the following test methods.

7) Solution viscosity

The solution viscosity of the curable resin composition was measured using an E-type viscometer at a measurement temperature: 25 ° C.

8) Bending strength and elongation at break

The test piece used in the bending test was a varnish of a curable resin composition was loaded on a die below a vacuum press molding machine, and the solvent was evaporated under heating and vacuum. After that, the upper mold was loaded, and heated and pressed under vacuum, and held at 200 ° C. for 1 hour, thereby forming a flat plate having a thickness of 1.0 mm. A test piece having a width of 5.0 mm, a thickness of 1.0 mm, and a length of 120 mm was prepared from the flat plate obtained by the forming, and a bending test was performed. The bending strength and bending elongation of the produced bending test piece were measured using a universal testing device. In addition, the bending strength and the elongation at break at break are evaluated as ○ when the measured value with respect to the reference formulation is less than ± 10%, and when the measured value with respect to the reference formulation is 10% or more. The evaluation was ◎, and the value of the range of -10% to -20% with respect to the reference formulation was evaluated as △, and the value of the measurement with respect to the reference formulation was -20% or less. Is ×.

9) Coefficient of linear expansion and glass transition temperature

The test piece used for the test of the coefficient of linear expansion of the curable resin composition and the glass transition temperature was a varnish of the curable resin composition was loaded on a flat-plate-shaped mold below a vacuum press molding machine, and heated under vacuum. Solvent devolatilization. Thereafter, the upper mold was loaded with a spacer of 0.2 mm, heated and pressed under vacuum, and held at 200 ° C. for 1 hour, thereby forming a flat plate having a thickness of 0.2 mm. A test piece having a width of 3.0 mm, a thickness of 0.2 mm, and a length of 40 mm was prepared from the flat plate obtained by forming, and was set only on a chuck above a TMA (thermo-mechanical analysis device) under a nitrogen gas flow at a heating rate 10 ° C / min until 220 ° C, and then The residual solvent was removed by performing a heat treatment at 220 ° C for 20 minutes, and the forming strain in the test piece was removed. After the TMA was left to cool to room temperature, the lower side of the test piece in the TMA measuring device was also set on the analysis probe, and the temperature was increased from 10 ° C / min to 30 ° C to 360 ° C under a nitrogen gas flow. Scan the measurement and calculate the linear expansion coefficient based on the dimensional change from 0 ° C to 40 ° C.

In addition, as for the glass transition temperature, the test piece was set on a DMA (Dynamic Viscoelastic Device) measurement device, and scanning was performed from 30 ° C to 320 ° C at a temperature increase rate of 3 ° C / min under a nitrogen gas stream. It measured and calculated | required Tg from the peak top of a tan (delta) curve.

10) Dielectric constant and dielectric loss tangent

According to the JIS C2565 standard, a cavity resonator method dielectric constant measuring device manufactured by AET Co., Ltd. was used, and a hardened flat plate test piece was stored in a room at 23 ° C. and 50% humidity for 24 hours after absolute drying. Dielectric constant and dielectric loss tangent at 18GHz.

In addition, the hardened plate test piece was left at 85 ° C. and a relative humidity of 85% for 2 weeks, and then the dielectric constant and the dielectric loss tangent were measured, and the dielectric constant and the dielectric loss tangent after the moist heat resistance test were measured.

11) Copper foil peeling strength

A glass cloth (E glass, basis weight: 71 g / m ² ) was immersed in a varnish of a thermosetting resin composition to be impregnated, and dried in an air oven at 80 ° C. for 10 minutes. At this time, adjustment was performed so that the resin content (RC) of the obtained prepreg became 50 wt%.

Using this prepreg, a plurality of pieces of the hardenable composite material are superimposed so that the thickness after forming becomes about 0.6 mm to 1.0 mm, and copper foils (trade names F2-) with a thickness of 18 μm are placed on both sides thereof. WS copper foil, Rz: 2.0 μm, Ra: 0.3 μm), and was formed and hardened by a vacuum press molding machine to obtain a laminated body for evaluation. The curing conditions were such that the temperature was raised at 3 ° C./min, and the temperature was maintained at 200 ° C. for 60 minutes under a pressure of 3 MPa to obtain a copper-clad laminated board for evaluation.

A test piece having a width of 20 mm and a length of 100 mm was cut out of the laminated body hardened material obtained in the manner described above, and a parallel cut of 10 mm in width was cut into the copper foil surface, and then 50 mm in a direction of 90 ° with respect to the surface. The copper foil was continuously peeled at a rate of 1 / min, the stress at this time was measured with a tensile tester, and the minimum value of the stress was recorded as the copper foil peeling strength. (According to JIS C 6481).

The copper foil peel strength test after the moist heat resistance test was performed by leaving the test piece at 85 ° C. and a relative humidity of 85% for 2 weeks, and then measuring it in the same manner as described above.

12) Peeling strength of copper plating

． Production of laminated board with copper plating

The copper-clad laminated board prepared in the preceding paragraph was immersed in a 150 g / L aqueous solution of ammonium persulfate for 20 minutes at 40 ° C to remove the copper foil by etching.

Next, the laminated board without the sample was immersed in a Circuposit MLB Conditioner211 (manufactured by Rohm and Haas Japan Co., Ltd., trade name) in a swelling aqueous solution at 80 ° C. for 5 minutes by the dipping method. deal with. After further processing at room temperature under running water for 3 minutes, Circuposit MLB Promoter 213 (manufactured by Rohm and Haas Co., Ltd., Japan) was used as a strong alkaline solution of permanganate, and similarly, a dipping method was performed at 80 ° C. for 10 minutes.

Then, using MLB Neutralizer 216 (manufactured by Rohm and Haas Co., Ltd., trade name) as a neutralizing solution, a dipping method was performed at 40 ° C. for 5 minutes. After treatment at room temperature under running water for 3 minutes, CLC-501 (trade name, manufactured by Hitachi Chemical Industry Co., Ltd.) was used at 60 ° C for 5 minutes using a conditioning solution, and then washed under running water in a prepreg. PD-201 (trade name, manufactured by Hitachi Chemical Industries, Ltd.) in an aqueous solution, treated at room temperature for 3 minutes, and then in an aqueous solution containing a metal palladium solution HS-202B (trade name, manufactured by Hitachi Chemical Industries, Ltd.) It was treated at room temperature for 10 minutes, washed with water, and then treated in an aqueous solution of an activation treatment solution ADP-501 (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 5 minutes at room temperature. In addition, Cust-201 was used as an electroless copper plating solution, and immersion treatment was performed at room temperature for 15 minutes by the immersion method, thereby forming base copper having an electroless copper thickness of 0.5 μm on both sides of the laminated board, and further using electrolytic copper plating. Thicken until the copper thickness is 20 μm.

Furthermore, from the test laminated plate hardened product with a plating layer, a wire having a copper width of 10 mm and a length of 100 mm was processed by etching, and one end was peeled off and clamped by a jig in accordance with JIS-C-6421. The lowest value of the load when peeling about 50 mm in the vertical direction at room temperature is recorded as the copper peeling strength.

13) Formability

The copper-clad laminated board for evaluation which was formed in the foregoing paragraph was produced in a grid pattern. The core material was patterned into a line width (L) of 0.5 mm and a line interval (S) of 1.0 mm (L / S = 0.5 / 1.0 mm). The core material was subjected to a blackening treatment, and then a prepreg was further laminated thereon, and the molding was performed twice to prepare a laminated substrate for evaluation with an inner layer having a lattice pattern. For the produced laminated substrate for evaluation, for example, it was confirmed whether defects such as voids formed due to insufficient fluidity of the resin varnish were generated. After that, the laminated substrate for evaluation was immersed in boiling water for 4 hours, and then immersed in a solder bath at 280 ° C. At this time, the existence of voids could not be confirmed, and even after immersion in the solder bath, the occurrence of defects such as swelling, interlayer peeling, and white spots (white spots) was evaluated as "○", and voids, swelling, and interlayers could be confirmed. The producer of either peeling or white spots (white spots) was evaluated as "×".

<Explanation of symbols in the table>

Modified PPE-A: Polyphenylene oligomer with vinyl groups at both ends (Mn = 1160, manufactured by Mitsubishi Gas Chemical Co., Ltd., 2,2 ', 3,3', 5,5'-hexamethyl The reaction product of biphenyl-4,4'-diol. 2,6-dimethylphenol polycondensate and chloromethylstyrene)

Modified PPE-B: Polyphenylene oligomer with vinyl at both ends (Mn = 2270, manufactured by Mitsubishi Gas Chemical Co., Ltd., 2,2 ', 3,3', 5,5'-hexamethyl The reaction product of biphenyl-4,4'-diol. 2,6-dimethylphenol polycondensate and chloromethylstyrene)

Modified PPE-C: Polyphenylene oligomer with vinyl at one end (Mn = 2340, polyphenylene ether (SA120 manufactured by SABIC Innovative Plastics)) and chloromethylstyrene reaction product)

TAIC: triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.)

DCP: Tricyclodecane dimethanol dimethacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

A-DCP: Tricyclodecane dimethanol diacrylate (made by Shin Nakamura Chemical Industry Co., Ltd.)

O-cresol novolac epoxy resin: Epotohto YDCN-700-3 (low viscosity type, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)

Bisphenol F type liquid epoxy resin: Epikote806L, Mw = 370 (manufactured by Japan Epoxy Resin Company)

Naphthalene skeleton liquid epoxy resin: EPICLON HP-4032D, Mw = 304 (manufactured by Di Edison)

Naphthol-type epoxy resin: ESN-475V, epoxy equivalent: 340 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.)

Bisphenol A liquid epoxy resin: Epikote828US, Mw = 370 (manufactured by Japan Epoxy Resin Company)

Modified PPE-D: Polyphenylene oligomer with epoxy groups at both ends (Mn = 1180, manufactured by Mitsubishi Gas Chemical Co., Ltd., 2,2 ', 3,3', 5,5'-Hexaline Reaction product of diphenyl-4,4'-diol. 2,6-dimethylphenol polycondensate and epichlorohydrin)

Biphenyl skeleton phenol resin: manufactured by Meiwa Chemical Co., Ltd., MEH-7851-S

Melamine skeleton phenol resin: manufactured by Qunrong Chemical Industry Co., Ltd., PS-6492

Allyl-containing skeleton phenol resin: made by Japan Epoxy Resin Company, YLH-903

Alicyclic skeleton acid anhydride: made by Shin Nippon Physicochemical Corporation, MH-700

Aromatic skeleton acid anhydride: manufactured by Sartomer. Japan, SMA RESIN EF60

Styrene-based copolymer: KRATON A1535 (Keteng Polymer Co., Ltd. (Made by Kraton Polymers LLC)

Phenoxy resin: "YL7553BH30" (a 1: 1 solution of 30% by mass of MEK and cyclohexanone) manufactured by Mitsubishi Chemical Corporation, with a weight average molecular weight of 37,000

Amorphous spherical silicon dioxide: manufactured by Admatechs, SE2050 SPE, with an average particle size of 0.5 μm (treated with a phenylsilane coupling agent)

Example 5

20 g of Copolymer-A obtained in Synthesis Example 1, 0.2 g of Percumyl P as a polymerization initiator, and 0.2 g of AO-60 as an antioxidant were dissolved in 8.6 g of toluene to obtain a curable resin composition (varnish A).

The prepared varnish A was added dropwise to the lower mold, and the solvent was devolatilized at 130 ° C under reduced pressure. Then, the molds were stacked in combination, and subjected to vacuum pressure pressing at 200 ° C and 3 MPa for 1 hour, and heat hardening. With respect to the obtained hardened plate test piece having a thickness of 0.2 mm, various characteristics including a dielectric constant and a dielectric loss tangent of 18 GHz were measured. In addition, after the hardened flat plate test piece was left at 85 ° C. and a relative humidity of 85% for 2 weeks, the dielectric constant and the dielectric loss tangent were measured, and the dielectric constant and the dielectric loss tangent after the moist heat resistance test were measured. Table 1 shows the results obtained by these measurements.

Examples 6 to 8 and Comparative Examples 3 to 4

A curable resin composition (varnish) was obtained in the same manner as in Example 5 except that the formulations shown in Table 1 were used. Moreover, in the same manner as in Embodiment 5, A hardened flat plate test piece was prepared by the formula, and the same items as in Example 5 were tested and evaluated. The results obtained by these tests are shown in Table 1.

Examples 9 to 19, Comparative Examples 5 to 8

A curable resin composition (varnish) was obtained by a method similar to Example 5 except that the formulations shown in Tables 2 and 3 were used. Further, a hardened flat plate test piece was produced in the same manner as in Example 5, and the same items as in Example 5 were tested. Evaluation. The results obtained by these tests are shown in Table 1. Furthermore, using the varnishes shown in these Examples and Comparative Examples, a prepreg, a copper-clad laminated board for testing, and a test tape were prepared according to the methods described in Test Methods 11) to 13). A laminated board having a plated layer was evaluated for copper foil peeling strength, copper plating peeling strength, and formability. The test results are shown in Tables 2 and 3.

Examples 21 to 30 and Comparative Examples 11 to 12

The copolymers A to F obtained in Synthesis Examples 1 to 6 were used to prepare a curable resin composition.

The copolymers, acrylates, polymerization initiators, and additives shown in Tables 4 and 5 were mixed at the ratios (weight ratios) shown in Tables 4 and 5 to prepare a curable resin composition. Here, the examples and comparative examples shown in Tables 4 and 5 except for Example 29, the resin composition obtained by mixing the formulations described in the table were directly formed into test pieces for evaluation. Regarding Example 29, in order to facilitate the dissolution of the stabilizer and the initiator, 30 parts by weight of toluene as a solvent was added to 100 parts by weight of the resin component, and the components were dissolved to prepare a resin varnish. The resin varnish was devolatilized under reduced pressure at 50 ° C., and the resin composition after removing the solvent was used to prepare a test piece.

The test piece was prepared by adding only a thermal initiator (Example 21 to Example 28, Comparative Example 11 to Comparative Example 12), the curable resin composition was loaded on a lower mold, and b-stage was performed under heating vacuum. Into. After the viscosity of the resin composition increases and becomes viscous, the upper mold is loaded on the lower mold, and the mold is loaded on a heating plate of a vacuum press molding machine, and is heated and pressed under vacuum, and maintained at 200 ° C for 1 hour. Thus, a hardened resin flat plate A1 having a thickness of 1.0 mm is formed. On the other hand, in the formulation (Example 29 to Example 30) containing an ultraviolet (UV) initiator, between two glass plates having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm, it was used A spacer made of 1.0 mm thick silicone rubber, with a gap of 1.0 mm being opened, is injected into a glass mold in which the outer periphery is fixed by a polyimide tape. After entering the composition, a high-pressure mercury lamp was used to irradiate one side of the glass mold with ultraviolet rays for a few seconds to carry out primary hardening. The glass mold was placed in an inert gas oven under a stream of nitrogen and heated at 200 ° C for 1 hour, thereby The hardened resin plate A2 is formed.

A test piece obtained by setting a cured resin flat plate A1 or a cured resin flat plate A2 having a thickness of 1.0 mm to a predetermined size is referred to as a test piece A.

A test piece obtained by setting a hardened resin flat plate B1 or a hardened resin flat plate B2 having a thickness of 0.2 mm obtained in the same manner as described above to a predetermined size is referred to as a test piece B.

The properties of these curable resin compositions and cured products were evaluated by the following test methods.

These measurement results are shown in Tables 4 and 5.

7) Solution viscosity

The solution viscosity of the curable resin composition (containing no solvent) was measured using an E-type viscometer at a measurement temperature: 25 ° C.

8) Bending strength and elongation at break

A test piece A having a width of 5.0 mm, a thickness of 1.0 mm, and a length of 120 mm was prepared. The bending strength and bending elongation were measured using a universal testing device. In addition, the bending strength and the elongation at break at break are evaluated as ○ when the measured value with respect to the reference formulation is less than ± 10%, and when the measured value with respect to the reference formulation is 10% or more. The evaluation was ◎, and the value of the range of -10% to -20% with respect to the reference formulation was evaluated as △, and the value of the measurement with respect to the reference formulation was -20% or less. Is ×.

9) Coefficient of linear expansion and glass transition temperature

A test piece B having a width of 3.0 mm, a thickness of 0.2 mm, and a length of 40 mm was prepared. The test piece was set only on a chuck above a TMA (thermo-mechanical analysis device), and heated to 220 ° C. at a heating rate of 10 ° C./min under a nitrogen gas flow, and further heat-treated at 220 ° C. for 20 minutes to perform a test piece. Removal of forming strains. After the TMA was left to cool to room temperature, the lower side of the test piece in the TMA measuring device was also set on the analysis probe, and the temperature was increased from 10 ° C / min to 30 ° C to 360 ° C under a nitrogen gas flow. Scan the measurement and calculate the linear expansion coefficient based on the dimensional change from 0 ° C to 40 ° C. The glass transition temperature was determined by a tangent method.

In addition, since the glass transition temperature was not observed in all Examples and Comparative Examples, the description is omitted.

10) Measurement of refractive index

Using a test piece A having a thickness of 1.0 mm, the refractive index and Abbe number were measured by an Abbe refractometer (manufactured by Atago).

12) Hue

The test piece A having a thickness of 1.0 mm was used to measure with a color difference meter (trade name "Model TC-8600", manufactured by Tokyo Denshoku Co., Ltd.), and its YI value was indicated.

13) Haze (turbidity) and total light transmittance

The test piece B having a thickness of 0.2 mm was used to measure haze (turbidity) and total light transmittance using an integrating sphere-type light transmittance measuring device (manufactured by Nippon Denshoku Co., Ltd., SZ-Σ90).

14) Demoldability, mold reproducibility, burrs and leakage

In the formulation (Example 21 to Example 28, Comparative Example 11 to Comparative Example 12) in which only a thermal initiator was added, a curable resin composition was loaded on a lower mold, and b-staged under heating vacuum. After the viscosity of the resin composition increases and becomes viscous, the upper mold is loaded on the lower mold, and the mold is loaded on a heating plate of a vacuum press molding machine, and is heated and pressed under vacuum, and maintained at 200 ° C for 1 hour. On the other hand, in the formulation (Examples 29 to 30) containing a UV initiator, the curable resin composition was loaded on a mold having a cavity having a spherical lens shape with a diameter of 3.0 mm, and An upper mold made of glass is mounted on a lower mold, and the upper surface of the upper mold made of glass is irradiated with ultraviolet rays for several seconds by a high-pressure mercury lamp. The glass mold is then hardened once. The glass mold is placed in an inert gas oven under a stream of nitrogen. By heating at 200 ° C for 1 hour, a spherical lens having a diameter of 3.0 mm was molded. The molding of this spherical lens was repeated five times, and the mold release property was evaluated by the ease with which the cured resin lens was released from the mold.

○ …… Good release from the mold

△ ……

× …… Difficult demoulding or mold residue

The mold reproducibility was evaluated by observing the surface shape of the hardened resin lens and the surface shape of the mold.

○ …… Good reproducibility

× …… Poor reproducibility

Burrs and leaks occur when the hardened resin lens is released from the mold. The size of the burr generated outside the product part of the molded product and the degree of resin leakage into the gap of the mold were evaluated.

○ …… The size of the burr is less than 0.05mm, and the leakage of resin is less than 1.0mm

△ …… The size of the burr is less than 0.2mm, and the leakage of resin is less than 3.0mm

× …… The size of the burr is 0.2mm or more, and the leakage of resin is 3.0mm or more

15) Reflow heat resistance

Using a test piece A having a thickness of 1.0 mm, a spectrophotometer CM-3700d (manufactured by Konica Minolta) was used to measure the spectral transmittance at a wavelength of 400 nm. The measurement time points were set before the heat resistance test for post-curing at 190 ° C for 60 minutes, and after the heat resistance test for 8 minutes at 260 ° C in an air oven.

<Explanation of symbols in the table>

Fancryl FA-BZA: manufactured by Hitachi Chemical Industries, Ltd., benzyl acrylate

Fancryl FA-302A: manufactured by Hitachi Chemical Industries, Ltd., o-phenylphenoxyethyl acrylate

Light Acrylate PO-A: manufactured by Kyoeisha Chemical Co., Ltd., phenoxyethyl acrylate

Ogsol EA-0200: Acrylate containing osmium skeleton, manufactured by Osaka Gas Chemicals Co., Ltd.

Light Acrylate TMP-A: Trimethylolpropane triacrylate manufactured by Kyoeisha Chemical Co., Ltd.

Adekastab AO-412S: manufactured by ADEKA Corporation, pentaerythritol-tetrakis (dodecylthiopropionate)

Adekastab AO-60: manufactured by Aideco Co., Ltd., pentaerythritol tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate]

Perbutyl O: manufactured by Japan Oil Co., Ltd., tert-butyl peroxy-2-ethylhexanoate

Irgacure184: manufactured by Ciba Fine Chemicals, 1-hydroxy-cyclohexyl-phenyl-one

Synthesis Example 7

50 parts by weight of propylene glycol monomethyl ether acetate and 19 parts by weight of methyl lactate were added to a flask equipped with a stirrer, a cooling tube, a gas introduction tube, a dropping funnel, and a thermometer. Quantities are stirred while introducing nitrogen. The temperature was raised to 65 ° C, and 45 parts by weight of methyl methacrylate, 35 parts by weight of butyl acrylate, 17 parts by weight of 2-hydroxyethyl methacrylate, 13 parts by weight of methacrylic acid, and 2 were added dropwise over 3 hours. After mixing a mixture of 3 parts by weight of '-azobis (2,4-dimethylvaleronitrile), 49 parts by weight of propylene glycol monomethyl ether acetate, and 20 parts by weight of methyl lactate, the mixture was stirred at 65 ° C for 3 hours. The solution was further stirred at 95 ° C. for 1 hour to obtain a solution of the copolymer G (solid content: 45% by mass). The Mn of the obtained copolymer G was 16,700, Mw was 38,100, Mw / Mn was 2.28, and the acid value was 79 mgKOH / g.

Manufacturing example 1

While stirring, 10 parts by weight of the copolymer A as the component (A), and 62 parts by weight of the solution of the interpolymer G as the component (45% by mass) (28% by mass of the solid content) ), 33 parts by mass of (meth) acrylic acid urethane ("U-200AX" manufactured by Shin Nakamura Chemical Industry Co., Ltd.) having a polyester skeleton as a component (B), and ( 15 parts by mass of meth) acrylic acid urethane ("UA-4200" manufactured by Shin Nakamura Chemical Industry Co., Ltd.) as a component (F) using methyl ethyl ketoxime to protect hexamethylene diisocyanate 20 parts by mass of a polyfunctional blocked isocyanate solution of an isocyanurate type trimer (solid content: 75% by mass) ("Sumidur BL3175" manufactured by Sumika Bayer Urethane (Stock)) (15 parts by mass of solid content), 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane as a photopolymerization initiator of component (C) 1 part by mass of 1-ketone ("Irgacure 2959" manufactured by Ciba. Japan (Stock)), bis (2,4,6-trimethylbenzyl) phenylphosphine oxide ("Irgacure819" manufactured by Ciba Corporation) and 23 parts by mass of propylene glycol monomethyl ether acetate as an organic solvent for dilution are mixed. After performing pressure filtration using a polytetrafluoroethylene filter having a pore size of 2 μm, defoaming was performed under reduced pressure to obtain a resin varnish W-I for coating formation.

Manufacturing example 2

Using the applicator, the varnish WI was applied to a non-treated surface of a PET film ("Cosmoshine A4100" manufactured by Toyobo Co., Ltd., thickness: 50 μm), dried at 100 ° C for 20 minutes, and then applied. As a cover film, a surface release-treated PET film ("Purex A31" manufactured by Teijin Du Pont Films (Stock Co., Ltd.) with a thickness of 25 µm) was obtained to obtain a resin film FI for cladding formation. At this time, the thickness of the resin layer was adjusted so that the film thickness after curing became 20 μm in the resin film for forming the lower cladding layer and 60 μm in the resin film for forming the upper cladding layer.

Manufacturing example 3

15 parts by weight of copolymer A, 33.3 parts by weight of solution of copolymer G (15 parts by weight of solid content), 2-methacryloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd.) `` Light Ester HO-MS '') 10 parts by weight, 20 parts by weight of bisphenol A (meth) acrylic acid urethane ("U-108A" manufactured by Shin Nakamura Chemical Industry Co., Ltd.) having a polyester skeleton 20 parts by weight of ethylene oxide (Ethylene Oxide, EO) adduct diacrylate ("Fancryl FA-321A" manufactured by Hitachi Chemical Industries, Ltd.), and a polyfunctional blocked isocyanate solution (solid content: 75% by weight) ) ("Sumidur BL3175" manufactured by Sumika Bayer Polyurethanes Co., Ltd.) 20 parts by weight (15 parts by weight of solid content), and further 1- [4- (2-hydroxyethoxy) Phenyl] -2-hydroxy-2-methyl-1-propane-1-one (manufactured by BASF Japan (stock); Irgacure 2959) 1 part by weight, bis (2,4,6-trimethylbenzene) 1 part by weight of formamyl) phenylphosphine oxide (manufactured by BASF, Japan; Irgacure 819), and 19 parts by weight of propylene glycol monomethyl ether acetate were mixed while stirring. After performing pressure filtration using a polytetrafluoroethylene filter having a pore size of 2 μm, defoaming was performed under reduced pressure to obtain a resin varnish W-II for core formation.

Manufacturing Example 4

Using a coater, apply the resin varnish W-II for core formation to a non-treated surface of a PET film ("Cosmoshine A1517" manufactured by Toyobo Co., Ltd., thickness: 16 μm), and dry at 80 ° C for 10 minutes. After drying at 100 ° C for 10 minutes, a surface release-treated PET film (manufactured by Teijin DuPont Films; Purex A31 with a thickness of 25 μm) was applied as a protective film to obtain a resin film F-II for core formation. . At this time, the thickness of the resin layer was adjusted so that the film thickness after curing became 50 μm.

Example 31

Using a roll laminator, the resin film F-I for forming the lower cladding layer from which the protective film was removed was laminated on a PET film (50 μm thick) under a pressure of 0.5 MPa and a temperature of 80 ° C. Furthermore, pressure bonding was performed using a vacuum pressure type laminator under conditions of a pressure of 0.4 MPa and a temperature of 80 ° C.

Then, an ultraviolet exposure machine was used to irradiate 2000 mJ / cm ² of ultraviolet rays (wavelength 365 nm), and then the support film was removed. Then, it heat-hardened at 160 degreeC for 1 hour, and the lower cladding layer 4 was formed.

Next, using a roll laminator, the core film-forming resin film F-II from which the protective film was removed was laminated on the lower cladding layer 4 under a pressure of 0.5 MPa and a temperature of 80 ° C. Furthermore, using the vacuum pressure type laminator, pressure bonding was performed under conditions of a pressure of 0.4 MPa and a temperature of 80 ° C.

Next, the core portion 2 (core pattern) was exposed by irradiating ultraviolet rays (wavelength 365 nm) at 1000 mJ / cm ² with a UV exposure machine through a negative mask having a width of 50 μm. After heating after exposure at 80 ° C., the support film was removed, and development was performed using propylene glycol monomethyl ether acetate / N, N-dimethylacetamide (70/30 mass ratio). After washing with propylene glycol monomethyl ether acetate, washing with 2-propanol was performed. After drying, it was heat-hardened at 160 ° C for 1 hour.

Next, using a vacuum press type laminator, the resin film FI for forming the upper cladding, from which the protective film was removed, was laminated on the core 2 and the lower cladding 4 under a pressure of 0.4 MPa and a temperature of 100 ° C. . The upper cladding layer 3 was formed by irradiating ultraviolet rays (wavelength: 365 nm) at 2000 mJ / cm ² and removing the supporting film, followed by heating and curing at 160 ° C. for 1 hour. Thereafter, the surface release-treated PET film was removed, and the optical waveguide tube 1 shown in FIG. 1 (d) was obtained. Thereafter, a dicing saw was used to cut out a flexible optical waveguide having a length of 10 cm.

The obtained flexible optical waveguide was evaluated as follows.

[Measurement of light propagation loss]

Vertical Cavity Surface Emitting Laser (VCSEL) ("FLS-300-01-VCL" manufactured by EXFO) was used as the light source with light having a wavelength of 850 nm as the center wavelength, and light receiving was used. Sensor "Q82214" manufactured by Advantest (share), incident fiber (GI-50 / 125 multimode fiber, NA = 0.20), and outgoing fiber (SI-114 / 125, NA = 0.22) Light Propagation Loss of a Flexible Optical Waveguide. The light propagation loss was calculated by dividing the measured value of the light loss (dB) by the length of the optical waveguide tube (10 cm), and evaluated based on the criteria shown in Table 8.

[High temperature and high humidity storage test]

For the obtained flexible optical waveguide, a high-temperature and high-humidity testing machine ("PL-2KT" manufactured by Espec) was used in accordance with the conditions of the JPCA standard (JPCA-PE02-05-01S). Next, a high-temperature and high-humidity standing test was performed at a temperature of 85 ° C. and a humidity of 85% for 1,000 hours.

Using the same light source, light receiving element, incident fiber, and output fiber as described above, the light propagation loss of the light-guide tube after the high-temperature and high-humidity placement test was measured, and evaluated according to the criteria shown in Table 8.

[Temperature cycle test]

For the obtained flexible optical waveguide, a temperature cycle tester ("ETAC WINTECH NT1010" manufactured by Kusumoto Chemical Co., Ltd.) was used, and the temperature was -55 in accordance with the JPCA standard (JPCA-PE02-05-01S). Temperature cycling test between ℃ and 125 ℃ 1000 times. Table 6 shows the detailed temperature cycle test conditions.

Using the same light source, light receiving element, incident fiber, and output fiber as described above, the light propagation loss of the light guide tube after the temperature cycle test was performed was evaluated using the criteria shown in Table 8.

[Reflow test]

For the obtained flexible optical waveguide, a reflow tester ("Salamander XNA-645PC" manufactured by Furukawa Electric Industry Co., Ltd.) was used in accordance with the Institute of the Interconnecting and Packing Electronic Circuit, Under the conditions of IPC) / JEDEC J-STD-020B, a reflow test with a maximum temperature of 265 ° C was performed 3 times in a nitrogen environment. The detailed reflow conditions are shown in Table 7, and the temperature distribution in the reflow furnace is shown in FIG. 2.

Using the same light source, light-receiving element, incident fiber, and exit fiber as described above, the light propagation loss of the light-guide tube after the reflow test was performed was evaluated using the criteria shown in Table 8.

The evaluation of the flexible optical waveguide obtained in Example 31 is shown in Table 9.

[Industrial availability]

The hardened material obtained from the terminal modified soluble polyfunctional vinyl aromatic copolymer or the material containing the same has improved heat resistance, compatibility, and toughness, and is excellent in low dielectric properties. Insulating materials or materials facing the laminate are useful. In addition, the curable resin composition of the present invention is excellent in transparency, heat resistance, and toughness, and can form a high-precision thick film. It is useful not only as a curable resin composition in a transparent material, but also for forming an optical waveguide. Useful.

Claims (26)

A terminally modified soluble polyfunctional vinyl aromatic copolymer includes a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit, and is composed of the following formula (2) and the following The copolymer of a terminal group represented by the formula (3) is characterized in that it is solvent-soluble and polymerizable, (Here, R ¹ represents a hydrocarbon group having 1 to 18 carbons or hydrogen, R ² to R ³ represent a hydrocarbon group having 1 to 18 carbons, and R ⁴ represents hydrogen or methyl). The terminally modified soluble polyfunctional vinyl aromatic copolymer according to item 1 of the scope of the patent application, wherein the divinyl aromatic compound (a) unit includes a structural unit without a vinyl group and has one ethylene The structural unit of the base. The terminal modified soluble polyfunctional vinyl aromatic copolymer described in item 1 of the patent application range has a number average molecular weight (Mn) of 300 to 100,000 and a molecular weight distribution (Mw / Mn) of 100.0 or less. The terminal modified soluble polyfunctional vinyl aromatic copolymer according to any one of claims 1 to 3 in the scope of the patent application, wherein the amount of introduction of the terminal group represented by the formula (3) (c1 ) Satisfies the following formula (4) (c1) ≧ 1.0 (units / molecule) (4), the Mohr fraction (a) of the structural unit derived from the divinyl aromatic compound in the copolymer, and The molar fraction (b) of the structural unit of the vinyl aromatic compound satisfies the following formula (5): 0.05 ≦ (a) / {(a) + (b)} ≦ 0.95 (5), and from the formula (2) ) And the Mohr fraction (c) of the terminal group represented by the formula (3) satisfy the following formula (6) 0.005 ≦ (c) / {(a) + (b)} <2.0 (6) and are soluble In toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. A method for producing a terminally modified soluble polyfunctional vinyl aromatic copolymer, which is manufactured as described in item 1 of the scope of application for a patent, which is characterized in that: A divinyl aromatic compound (a) and a monovinyl aromatic compound (b) are present in the presence of one or more catalysts (d) in the group consisting of a free Lewis acid catalyst, an inorganic strong acid, and an organic sulfonic acid. ), Polymerizing with the (meth) acrylate compound (c) represented by the following formula (1), (Here, R ¹ represents a hydrocarbon group having 1 to 18 carbons or hydrogen, R ² to R ³ represent a hydrocarbon group having 1 to 18 carbons, and R ⁴ represents hydrogen or methyl). The method for producing a terminally modified soluble polyfunctional vinyl aromatic copolymer according to item 5 of the scope of the patent application, wherein the method for producing a divinyl aromatic compound (a) and a monovinyl aromatic compound (b) 100 mol% in total, using 5 mol% to 95 mol% of divinyl aromatic compound (a), 95 mol% to 5 mol% of monovinyl aromatic compound (b) A measuring body of 100 mol is used, and the (meth) acrylate compound (c) represented by the formula (1) is used in a range of 0.5 mol to 500 mol, compared to the (meth) acrylate compound (c) 1. For Moore, the catalyst (d) is 0.001 Moore to 10 Moore, and the polymerization raw materials containing these are polymerized in a homogeneous solvent having a dielectric constant of 2.0 to 15.0. A hardenable composition, comprising: a terminally modified soluble polyfunctional vinyl aromatic copolymer and a radical polymerization initiator as described in item 1 of the scope of patent application. The hardenable composition according to item 7 of the scope of patent application, further comprising modified polyphenylene ether (XC). The hardenable composition according to item 7 or item 8 of the scope of the patent application, further comprising an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, and two in one molecule. The epoxy resin having the above epoxy group and cyanurate structure, and / or one or more epoxy groups in the group consisting of epoxy resins having two or more epoxy groups and alicyclic structure in one molecule Resin (XD), and hardener (XE). The hardened | cured material is hardened | cured by the hardening | curing composition as described in any one of Claims 7-9. A film formed by forming the curable composition according to any one of claims 7 to 9 of the scope of patent application into a film shape. A hardenable composite material, comprising the hardenable composition and the substrate according to any one of items 7 to 9 of the scope of application for a patent, characterized in that it contains a base in a proportion of 5 to 90% by weight. material. A hardened composite material, which is obtained by hardening the hardenable composite material described in item 12 of the scope of patent application. A laminated body, comprising: a layer of a hardenable composite material and a metal foil layer according to item 12 of the scope of patent application. A metal foil with a resin, characterized in that a film made of the curable composition according to any one of claims 7 to 9 of the scope of patent application is provided on one side of the metal foil. A varnish for a circuit board material, which is obtained by dissolving a hardenable composition according to any one of claims 7 to 9 in an organic patent application in an organic solvent. A curable resin composition comprising a component (A), which comprises a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit, and is composed of the following formula (2) and A copolymer of a terminal group represented by the following formula (3), and a polymerizable and solvent-soluble terminally modified soluble polyfunctional vinyl aromatic copolymer; (Here, R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms or hydrogen, R ² to R ³ represents a hydrocarbon group having 1 to 18 carbon atoms, and R ⁴ represents hydrogen or methyl group) (B) component: 1 or more in the molecule One or more vinyl compounds having an unsaturated group; and (C) a component: a radical polymerization initiator; and (A) a compounded amount of 5 to 94.9% by weight, and (B) a compounded amount of 5.0% to 85% by weight, and the blending amount of the component (C) is 0.1% to 10% by weight. The curable resin composition according to item 17 of the scope of patent application, wherein the component (B) contains one or more (meth) acrylates having one or more (meth) acrylfluorenyl groups in a molecule. The curable resin composition according to item 17 of the scope of application for a patent, wherein the component (B) contains a (meth) acrylate having a hydroxyl group and / or a carboxyl group in a molecule. A curable resin composition for forming an optical waveguide, characterized in that the curable resin composition according to item 17 of the scope of patent application is used for forming an optical waveguide. The curable resin composition according to item 17 of the scope of application for a patent, wherein the component (C) contains a photoradical polymerization initiator. The curable resin composition according to item 17 of the scope of patent application, wherein the component (B) contains a vinyl compound having a structural unit represented by the following general formula (16) or general formula (17), The hardened vinyl polymer produced by the vinyl compound, (In the formula, R ⁵ represents a hydrogen atom or a methyl group, and X ¹ represents that it may contain one or more selected from the group consisting of a single bond, or an ester bond, an ether bond, a thioester bond, a thioether bond, and a amide bond. A divalent organic group having 1 to 20 carbon atoms in the bond; R ⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms) (In the formula, R ⁷ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R ⁸ represents a hydrogen atom or a methyl group, and X ² represents that it may contain a single bond or an ester bond, an ether bond, or a thioester. One or more bonds in the group consisting of a bond, a thioether bond, and a fluorene bond; a divalent organic group having 1 to 20 carbon atoms; R ⁹ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms ). A resin film for forming a light waveguide is formed using the curable resin composition according to any one of claims 17 to 22 of the scope of patent application. An optical waveguide includes a core portion and / or a cladding layer formed using the curable resin composition according to any one of claims 17 to 22 of the scope of patent application. An optical waveguide includes a core portion and / or a cladding layer formed using the resin film for forming an optical waveguide as described in item 23 of the scope of patent application. According to the optical waveguide tube described in item 24 or item 25 of the scope of application for a patent, the light propagation loss in a light source with a wavelength of 850 nm is 0.3 dB / cm or less.