KR102498471B1 - Terminal-modified soluble polyfunctional vinyl aromatic copolymer, and curable resin composition and optical waveguide produced using same - Google Patents

Abstract

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 are provided. A divinyl aromatic compound (a), a monovinyl aromatic compound (b), and a (meth)acrylic acid ester compound (c) are mixed with at least one catalyst (d) selected from the group consisting of a Lewis acid catalyst, an inorganic strong acid, and an organic sulfonic acid. A copolymer obtained by polymerization in the presence of a terminal modified soluble polyfunctional vinyl aromatic copolymer having a terminal group derived from a (meth)acrylic acid ester compound (c) at a part of the terminal of the copolymer.

Description

Terminal-modified soluble polyfunctional vinyl aromatic copolymer, curable resin composition, and optical waveguide using the same

The present invention relates to a novel terminal-modified soluble polyfunctional vinyl aromatic copolymer having improved heat resistance, compatibility and toughness, and a curable resin composition. In particular, a curable resin composition containing a novel terminal-modified soluble polyfunctional vinyl aromatic copolymer and useful as a substrate material in the field of advanced electronic devices in fields requiring a high degree of reliability, curable composite materials and laminates thereof, and also transparency, light It relates to a resin composition for forming an optical waveguide, a resin film for forming an optical waveguide, and an optical waveguide using the same, which are excellent in propagation loss, heat discoloration resistance, environmental reliability, and optical transmission loss.

With the recent increase in information communication volume, information communication in the high frequency band is actively conducted, and in order to reduce transmission loss in the high frequency band, more excellent electrical characteristics, especially, it has a low permittivity and a low dielectric loss tangent, especially the dielectric after water supply. Electrical insulating materials with little change in properties are required. In addition, since printed circuit boards or electronic components using these electrical insulating materials are exposed to high-temperature solder reflow during mounting, materials with high heat resistance, that is, exhibiting a high glass transition temperature, are required. Particularly in recent years, since lead-free solder having a high melting point is used due to environmental problems, a demand for an electrical insulating material having higher heat resistance has increased. In response to these demands, cured resins using vinyl compounds having various chemical structures have conventionally been proposed.

As such a cured resin, for example, in Patent Document 1, a soluble polyfunctional obtained by polymerizing a divinyl aromatic compound and a monovinyl aromatic compound in an organic solvent in the presence of a Lewis acid catalyst and an initiator having a specific structure at a temperature of 20 to 100°C. Vinyl aromatic copolymers are disclosed. In addition, in Patent Document 2, a monomer component containing 20 to 100 mol% of a divinyl aromatic compound is controlled by cationic polymerization at a temperature of 20 to 120 ° C. with a Lewis acid catalyst and an initiator having a specific structure in the presence of a quaternary ammonium salt. A process for preparing a soluble multifunctional vinyl aromatic copolymer having a molecular weight distribution is disclosed. The soluble polyfunctional vinyl aromatic copolymer obtained by the techniques disclosed in these two patent documents is excellent in solvent solubility and processability, and by using this, a cured product having a high glass transition temperature and excellent heat resistance can be obtained.

Since the soluble polyfunctional vinyl aromatic copolymer obtained by these techniques itself has a polymerizable double bond, curing it gives a cured product having a high glass transition temperature. Therefore, this cured product or soluble polyfunctional vinyl aromatic copolymer can be said to be a polymer or a precursor thereof having excellent heat resistance. Then, this soluble polyfunctional vinyl aromatic copolymer is copolymerized with another radically polymerizable monomer to give a cured product, but this cured product also becomes a polymer having excellent heat resistance.

However, from the viewpoint of the compatibility of the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 1 and Patent Document 2 with other curable resins and the heat discoloration resistance after curing, compatibility between highly polar epoxy compounds and phenol resins The solubility or solubility is not sufficient, and the thermal decomposition resistance to high process temperatures is also not sufficient. Therefore, depending on the type of epoxy compound or phenol resin, there are many cases in which an opaque composition is given, and it is difficult to make a uniform cured product of an epoxy compound or phenol resin and a soluble polyfunctional vinyl aromatic copolymer. This causes defects such as a small degree of freedom in formulation design and low toughness of the cured product, and there are cases in which defects such as expansion and peeling occur due to high thermal history around 280 to 300 ° C.

Further, Patent Document 3 is a copolymer obtained by copolymerizing a divinyl aromatic compound (a) and a monovinyl aromatic compound (b), wherein a chain hydrocarbon group or aromatic hydrocarbon group via an ether bond or a thioether bond is attached to a part of the terminal group. A soluble multifunctional vinyl aromatic copolymer having

However, since this soluble polyfunctional vinyl aromatic copolymer lacks toughness, sufficient mechanical properties cannot be obtained in the cured product of the curable composition, and therefore, in the cured composite product, problems such as insufficient interlayer peel strength and decrease in reliability are encountered. there was. In addition, it is described that an ester compound can be used as a cocatalyst, but specifically exemplified as usable ester compounds do not have a function of introducing a functional group to the terminal of a soluble polyfunctional vinyl aromatic copolymer such as ethyl acetate or methyl propionate. It was an ester compound that did not. For this reason, the terminal group of the soluble polyfunctional vinyl aromatic copolymer disclosed in Patent Document 3 is a chain hydrocarbon compound having an alcoholic hydroxyl group, an aromatic hydrocarbon compound, a chain hydrocarbon compound having a thioalcoholic mercapto group, and an aromatic hydrocarbon compound. It contained a chain hydrocarbon group or an aromatic hydrocarbon group via either a derived ether bond or a thioether bond as a terminal group.

On the other hand, in Patent Document 4 and Patent Document 5, polyfunctional vinyl aromatic copolymers having terminal groups derived from aromatic ether compounds, and soluble polyfunctional vinyl aromatic copolymers having terminal groups derived from thio(meth)acrylate-based compounds. Synthesis is disclosed. However, the soluble polyfunctional vinyl aromatic copolymers disclosed in these patent documents have improved toughness, but do not have low dielectric properties in the high frequency band in accordance with the recent increase in information communication volume, There was a problem that it could not be applied to the advanced technology field requiring the same high-performance and high-level electrical characteristics, thermal and mechanical characteristics. In addition, these soluble polyfunctional vinyl aromatic copolymers have a drawback that they cannot be used for substrate materials in fields requiring high reliability because the adhesion at the interface with the glass cloth is reduced after a wet heat history.

On the other hand, Patent Document 6 discloses a curable resin composition comprising a polyphenylene ether oligomer having vinyl groups at both ends, and a polyfunctional vinyl aromatic copolymer having structural units derived from monomers composed of divinyl aromatic compounds and ethylvinyl aromatic compounds. has been However, the curable resin composition using this soluble polyfunctional vinyl aromatic copolymer has a drawback that it cannot be used as a substrate material in the field of advanced electronic equipment because it has poor interlayer peel strength, plating peel strength, and dielectric properties after wet heat history.

In Patent Document 7, a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer composed of a divinyl aromatic compound and an ethylvinyl aromatic compound selected from the group consisting of an epoxy group, a cyanate group, a vinyl group, an ethynyl group, an isocyanate group and a hydroxyl group A curable resin composition comprising a thermosetting resin containing at least one functional group is disclosed. However, since the curable resin composition using this soluble polyfunctional vinyl aromatic copolymer lacks plating properties, there has been a problem that it cannot be applied to high-performance cutting-edge technical fields requiring a high degree of miniaturization.

However, in transmission of high-speed and high-density signals between electronic elements or between wiring boards, mutual interference or attenuation of signals becomes a barrier in transmission using conventional electric wiring, and the limits of high-speed and high-density are beginning to be seen. In order to overcome this problem, development of so-called optical interconnection technology, which is a technology for connecting electronic elements and wiring boards with light, is being developed. As an optical transmission path, polymer optical waveguides are attracting attention because of ease of processing, low cost, high flexibility in wiring, and high density.

As the form of the polymer optical waveguide, a rigid optical waveguide fabricated on a hard support substrate such as glass epoxy resin, which is assumed to be applied to an optoelectric hybrid substrate, or a flexible optical waveguide without a hard support substrate, which is assumed to be connected between boards, is suitable. It is considered to be

In addition, the flexibility of mounting can be further improved by forming an opto-electric composite flexible wiring board in which the flexible wiring board and the optical waveguide are integrally combined.

Polymer optical waveguides require transparency (low propagation loss) as well as heat resistance and environmental reliability from the viewpoints of the use environment of the device to which they are applied and component mounting. In addition, demands for toughness are also increasing from the viewpoints of strength and handleability of optical waveguides. In addition, regarding the optical waveguide manufacturing process, a method capable of easily forming a core pattern is required, and as one of the methods, a pattern formation method by exposure development widely used in a printed wiring board manufacturing process is mentioned. As such a material, an optical waveguide material containing a (meth)acrylic polymer (for example, see Patent Literatures 8 to 11) is known.

The optical waveguide materials described in Patent Literatures 8 and 9 can form a core pattern by exposure and development, have transparency at a wavelength of 850 nm, and have good light propagation loss after a high-temperature, high-humidity standing test, but evaluation of heat resistance, such as solder There is no specific description of test results such as light propagation loss after reflow test.

In addition, the optical waveguide material described in Patent Literature 10 exhibits excellent light transmission loss and has good heat resistance, but is soft and cannot satisfy toughness.

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

Japanese Unexamined Patent Publication No. 2004-123873 Japanese Unexamined Patent Publication No. 2005-213443 Japanese Unexamined Patent Publication No. 2007-332273 Japanese Unexamined Patent Publication No. 2010-229263 Japanese Unexamined Patent Publication No. 2010-209279 WO2005/73264 Japanese Unexamined Patent Publication No. 2006-274169 Japanese Unexamined Patent Publication No. 2006-146162 Japanese Unexamined Patent Publication No. 2008-33239 Japanese Unexamined Patent Publication No. 2006-71880 Japanese Unexamined Patent Publication No. 2007-122023

In view of this background art, the present invention provides a novel terminal-modified soluble polyfunctional vinyl aromatic copolymer with improved heat resistance, compatibility and toughness, and is useful as a substrate material in the field of advanced electronic devices requiring high reliability. A curable resin composition, a curable composite material and a laminate thereof, and a curable resin composition excellent in transparency, low light propagation loss, heat resistance, environmental reliability, and toughness, in particular, a curable resin for optical waveguides capable of forming optical waveguides with good productivity and workability. An object of the present invention is to provide a composition, a resin film for forming an optical waveguide, and an optical waveguide using the same.

As a result of repeated intensive studies, the present inventors have found that a specific terminal-modified soluble polyfunctional vinyl aromatic copolymer, one or more vinyl compounds having at least one unsaturated group in the molecule and having a specific terminal group, and a radical polymerization initiator. Curable resin composition discovered that it could solve the said subject, and reached this invention.

That is, the present invention is a copolymer having a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit, and terminal groups represented by the following formula (2) and the following formula (3), which are solvent soluble, It is a terminal modified soluble polyfunctional vinyl aromatic copolymer characterized by having polymerizability.

(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 a methyl group.)

[0021] The above-mentioned copolymer is preferably one in which the unit of the divinyl aromatic compound (a) contains a structural unit having no vinyl group and a structural unit having 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 preferably has an introduced amount (c1) of the terminal group represented by the above formula (3) of the following formula (4)

(c1)≥1.0 (piece/molecule) (4)

is satisfied, and the mole fraction (a) of the structural unit derived from the divinyl aromatic compound and the mole fraction (b) of the structural unit derived from the monovinyl aromatic compound in the copolymer are expressed by the following formula (5)

0.05≤(a)/{(a)+(b)}≤0.95 (5)

is satisfied, and the molar fraction (c) of the terminal groups represented by the above formulas (1) and (2) is expressed by the following formula (6)

0.005≤(c)/{(a)+(b)}<2.0 (6)

, and is also soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.

In addition, in the present invention, a divinyl aromatic compound (a) and a monovinyl aromatic compound (b) and a (meth)acrylic acid ester compound (c) represented by the following formula (1) are mixed with a Lewis acid catalyst, an inorganic strong acid and an organic sulfonic acid. A method for producing the terminal-modified soluble polyfunctional vinyl aromatic copolymer, characterized in that polymerization is performed in the presence of at least one catalyst (d) selected from the group consisting of.

(Here, R ¹ to R ⁴ are synonymous with formulas (2) and (3))

In the method for producing the copolymer, preferably 5 to 95 mol% of divinyl aromatic compound (a) and monovinyl aromatic compound relative to 100 mol% in total of divinyl aromatic compound (a) and monovinyl aromatic compound (b). 95 to 5 mol% of compound (b) is used, and 0.5 to 500 mol of (meth)acrylic acid ester compound (c) represented by the above formula (1) is added to 100 mol of all monomers, and catalyst (d) ( 0.001 to 10 moles per mole of meth)acrylic acid ester compound (c) are used, respectively, and polymerization raw materials containing these are polymerized in a uniform solvent having a dielectric constant of 2.0 to 15.0.

Further, the present invention is a curable composition characterized by containing 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 includes an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, an epoxy resin having two or more epoxy groups and a cyanurate structure in one molecule, and/or two or more epoxy groups and an alicyclic structure in one molecule. One or more types of epoxy resins (XD) selected from the group consisting of epoxy resins and a curing agent (XE) may be contained.

Moreover, this invention is the hardened|cured material obtained by hardening the said curable composition, or the film formed by shape|molding the said curable composition into a film shape.

Further, the present invention is a curable composite material comprising the curable composition and a base material, characterized in that the base material is contained in a proportion of 5 to 90% by weight, and is obtained by curing the curable composite material. It is a cured composite material, and a laminate characterized in that it has a layer of the cured composite material and a thin metal layer.

Further, the present invention is a metal foil with a resin characterized by having a film formed of the curable composition on one side of the metal foil, or a varnish for circuit board materials obtained by dissolving the curable composition in an organic solvent.

In addition, the present invention relates to divinyl aromatic compound (a), monovinyl aromatic compound (b) and (meth)acrylic acid ester compound (c) at least one selected from the group consisting of Lewis acid catalysts, inorganic strong acids and organic sulfonic acids. It is a copolymer obtained by reacting in the presence of a catalyst (d), and a word derived from the (meth)acrylic acid ester compound (c) represented by the formula (2) and formula (3) at a part of the terminal of the copolymer, respectively. It has a short term, the number average molecular weight Mn is 300 to 100,000, the molecular weight distribution (Mw/Mn) expressed by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is 100.0 or less, and the introduced amount of the terminal group (c1) is the following formula (3)

(c1)≥1.0 (unit/molecule) (3)

is satisfied, and the mole fraction (A) of the structural units derived from the divinyl aromatic compound and the mole fraction (B) of the structural units derived from the monovinyl aromatic compound in the copolymer are expressed by the following formula (4)

0.05≤(A)/{(A)+(B)}≤0.95 (4)

Satisfying, and the molar fraction (C) of the terminal group is expressed by the following formula (5)

0.005≤(C)/{(A)+(B)}<2.0 (5)

and is also a terminal-modified soluble polyfunctional vinyl aromatic copolymer characterized by being soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.

In addition, the present invention is a method for producing a copolymer by reacting a divinyl aromatic compound (a), a monovinyl aromatic compound (b) and a (meth)acrylic acid ester compound (c), wherein the divinyl aromatic compound (a) and 5 to 95 mol% of the divinyl aromatic compound (a) and 95 to 5 mol% of the monovinyl aromatic compound (b) are used with respect to the total of 100 mol% of the monovinyl aromatic compound (b), and further by the above formula (1) 0.5 to 500 moles of the (meth)acrylic acid ester compound (c) shown relative to 100 moles of all monomers and one or more catalysts (d) selected from the group consisting of Lewis acid catalysts, inorganic strong acids and organic sulfonic acids are used, , Polymerization is carried out at a temperature of 20 to 120 ° C. in a homogeneous solvent in which polymerization raw materials containing these are dissolved in a solvent with a dielectric constant of 2.0 to 15.0, and (meth) acrylic acid represented by the following formulas (2) to (3) is attached to the end of the copolymer. End-modified soluble polyfunctional vinyl aromatic, characterized by obtaining a copolymer having 1.0 (units/molecule) or more of terminal groups derived from ester-based compound (c) and soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform It is also a method for producing copolymers.

Moreover, this invention is (A) component: a copolymer which has a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit, and the terminal group represented by following formula (2) and following formula (3), , A solvent-soluble, terminally modified soluble polyfunctional vinyl aromatic copolymer having polymerizability,

Component (B): at least one vinyl compound having at least one unsaturated group in the molecule, and

(C) component: containing a radical polymerization initiator,

It is a curable resin composition characterized in that the blending amount of component (A) is 5 to 94.9 wt%, the blending amount of component (B) is 5.0 to 85 wt%, and the blending amount of component (C) is 0.1 to 10 wt%.

Component (A) is preferably a copolymer having a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit and terminal groups represented by the above formula (2) and the above formula (3), The divinyl 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), and the monovinyl aromatic compound It is preferable that the compound (b) unit has a structural unit represented by the following formula (b), is solvent-soluble, and is a terminal-modified soluble polyfunctional vinyl aromatic copolymer having polymerizability.

This is a divinyl aromatic compound (a), a monovinyl aromatic compound (b), and a (meth)acrylic acid ester compound (c) represented by the formula (1) selected from the group consisting of a Lewis acid catalyst, an inorganic strong acid, and an organic sulfonic acid. It is preferably a copolymer obtained by polymerization in the presence of one or more types of catalysts (d), but a copolymer obtained by polymerization under other raw materials and conditions may be used.

(Here, R ¹⁵ , R ¹⁶ , 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.)

Further, the present invention is a curable resin composition for forming an optical waveguide, characterized in that the curable resin composition is for forming an optical waveguide.

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

(Wherein, R ⁵ and R ⁸ represent a hydrogen atom or a methyl group, X ¹ and X ² are single bonds or 1 selected from the group consisting of ester bonds, ether bonds, thioester bonds, thioether bonds and amide bonds Represents a divalent organic group having 1 to 20 carbon atoms which may contain more than one kind of bond, and R ⁶ and R ⁹ represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.)

Further, the present invention is a resin film for forming an optical waveguide formed by using the curable resin composition for forming an optical waveguide. Further, the present invention is an optical waveguide having a core portion and/or a cladding layer formed by using the curable resin composition for forming an optical waveguide or the resin film for forming an optical waveguide. Preferably, the optical waveguide has an optical propagation loss of 0.3 dB/cm or less in a light source having a wavelength of 850 nm.

The cured product obtained from the terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention or a material containing the same has improved heat resistance, compatibility and toughness. Further, according to the production method of the present invention, the copolymer can be produced with high efficiency. In addition, by using the terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention as a curable compound, a cured product having a high molecular size and a free volume with a large molecular size and a low polar group is obtained, thereby providing a highly low dielectric property, It is possible to simultaneously realize good adhesion, plating properties and dielectric loss tangent characteristics after wet heat history.

In addition, the curable resin composition of the present invention is excellent in transparency, heat resistance and toughness, can form a high-precision thick film, is useful not only as a curable resin composition for transparent materials, but is particularly useful for forming optical waveguides, and has high productivity. It can be used as a resin composition or resin film for forming a high optical waveguide. In addition, by using such a resin composition or resin film for forming an optical waveguide, an optical waveguide excellent in transparency, heat resistance, environmental reliability and toughness can be obtained.

1 is a cross-sectional view explaining the shape of an optical waveguide.
Fig. 2 is a diagram showing a temperature profile in a reflow furnace in a reflow test.

The soluble polyfunctional vinyl aromatic copolymer of the present invention comprises a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit comprising a structural unit having no vinyl group and a structural unit having one vinyl group, As a copolymer having an end group represented by (2) and Formula (3), it is a solvent-soluble, terminal-modified soluble polyfunctional vinyl aromatic copolymer having polymerizability.

This terminal-modified soluble polyfunctional vinyl aromatic copolymer is a Lewis acid catalyst, a divinyl aromatic compound (a) and a monovinyl aromatic compound (b), and a (meth)acrylic acid ester compound (c) represented by the formula (1), It may be a copolymer obtained by polymerization in the presence of at least one catalyst (d) selected from the group consisting of inorganic strong acids and organic sulfonic acids.

In the formula, 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 a methyl group. Preferred R ¹ to ^{R 3} are alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl groups.

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

This copolymer has a structural unit derived from divinyl aromatic compound (a) and a structural unit derived from monovinyl aromatic compound (b). The mole fraction (a) of structural units derived from divinyl aromatic compound and the mole fraction (b) of structural units derived from monovinyl aromatic compound in the copolymer are (a)/{(a)+(b)} = 0.05 to 0.95 It is good to satisfy It is preferably 0.2 to 0.8, more preferably 0.3 to 0.7. If it is less than 0.05, heat resistance is lowered, so there is a risk that a good optical waveguide shape cannot be maintained due to heat history in the optical waveguide formation process and electric wiring formation. If it is larger than 0.95, the molecular weight of the copolymer tends to be too large, and the etching characteristics may be deteriorated due to the crosslinking density being excessively large, and it may be difficult to form an optical waveguide with excellent shape and low 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. Preferably, it is considered to have structural units represented by the formulas (a1), (a2) and (a3). Hereinafter, these structural units are referred to as units (a1) to (a3).

Structural units having one vinyl group, for example, units (a1) and (a3) impart polymerizability to the copolymer, make the copolymer multifunctional, and make it a curable resin. Unit (a2), which is a structural unit not having a vinyl group, imparts a crosslinking structure and increases branching, but if crosslinking proceeds excessively, it hardens and becomes solvent insoluble. is required to exist.

The content of the units (a1) and (a3) in the copolymer is 10 relative to the sum of the mole fraction (a) of the structural units derived from the divinyl aromatic compound and the mole fraction (b) of the structural units derived from the monovinyl aromatic compound. It is preferably to 60 mol%, preferably 15 to 50 mol%, and more preferably 20 to 40 mol%. The content of the unit (a2) is preferably 5 to 50 mol%, preferably 10 to 40 mol%. The molar ratio of units (a1) and (a3) is preferably in the range of 99.999:0.001 to 1:99. The unit (a1) in the copolymer is preferably in the range of 99.99:0.01 to 30:70 from the viewpoint that the polymerizability during curing is better than that of the unit (a3). More preferably, it is the range of 99.99:0.01 - 50:50.

From another point of view, the content of the structural unit having one vinyl group in the structural units derived from the divinyl aromatic compound is preferably 10 to 90 mol%, preferably 20 to 80 mol%, and more preferably 30 to 70 mol%. am. However, the content or degree of polymerization of this structural unit is controlled, indicating solvent solubility.

In the above formulas (a1), (a2) and (a3), R ¹⁵ , R ¹⁶ , and R ¹⁷ represent aromatic hydrocarbon groups having 6 to 30 carbon atoms, but since they are derived from divinyl aromatic compounds, they are understood from the description. do. In the 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, an alkoxy group having 1 to 6 carbon atoms, or a hydrogen atom; these are monovinyl aromatic compounds. Since it is derived from, it is understood from the description.

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

If the content is small, heat resistance is lowered due to a decrease in crosslinking density, making it difficult to maintain a good shape when subjected to heat history in an optical waveguide forming process or the like. It becomes difficult to form an optical waveguide or the like.

From another point of view, it is preferable to contain 30 to 90 mol% of the structural unit (a) with respect to 100 mol% of the total of all the structural units. The structural unit (a) contains a vinyl group as a cross-linking component for developing heat resistance, while the structural unit (b) derived from a monovinyl aromatic compound does not have it, thereby imparting moldability and the like.

The copolymer of the present invention is represented by the above formulas (2) and (3) derived from a (meth)acrylic acid ester compound (c) in addition to the structural unit derived from the divinyl aromatic compound (a) and the monovinyl aromatic compound (b), Z has an end group as a structural unit. If the molar ratio of each structural unit is (a), (b), and (c), the molar fraction of the terminal group (c)/{(a)+(b)} is 0.005 or more and less than 2.0, preferably. It is 0.01 to 1.5, more preferably 0.05 to 1.0.

A resin composition having low light loss, high toughness, excellent heat resistance, excellent compatibility with a (meth)acrylate compound, and excellent molding processability by introducing the terminal group at the end of the copolymer to satisfy the above relationship. Or you can do it as a product. When the molar fraction of the terminal group is small, compatibility with the (meth)acrylate compound and molding processability are reduced, and when it is large, dimensional change after being subjected to moist heat history is increased, and the above characteristics are deteriorated.

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

The Mn of the soluble polyfunctional vinyl aromatic copolymer (here, Mn is the number average molecular weight in terms of standard polystyrene measured using gel permeation chromatography) is preferably 300 to 100,000, preferably 400 to 50,000, more preferably It is 500 to 10,000. If Mn is too low, the amount of the monofunctional copolymer contained in the copolymer increases, so the heat resistance of the cured product tends to decrease. . The value of the molecular weight distribution (Mw/Mn) is preferably 100.0 or less, preferably 50.0 or less, and more preferably 1.5 to 10.0. Most preferably, it is 1.5 to 5.0. If this is too high, the processing properties of the copolymer tend to deteriorate and gelation tends to occur.

The soluble polyfunctional vinyl aromatic copolymer is soluble in a solvent selected from toluene, xylene, tetrahydrofuran, dichloroethane or chloroform, but is advantageously soluble in any of these solvents. Here, soluble in a solvent means that 5 g or more, preferably 10 g or more, is dissolved in 100 g of the solvent at 25°C. In order to obtain a solvent-soluble multifunctional copolymer, it is necessary to polymerize the divinyl aromatic compound so that a part of the vinyl groups of the divinyl aromatic compound remain uncrosslinked and have an appropriate degree of crosslinking. The polymerization method is described later.

Soluble polyfunctional vinyl aromatic copolymers have high compatibility with (meth)acrylate-based compounds because their terminals are modified with the terminal groups. Therefore, when the curable resin composition containing a (meth)acrylate-based compound is cured, it becomes a product excellent in uniform curability and transparency.

Next, a production method capable of advantageously producing a terminal-modified soluble polyfunctional vinyl aromatic copolymer will be described.

This copolymer is prepared by combining a divinyl aromatic compound (a) and a monovinyl aromatic compound (b) with a (meth)acrylic acid ester compound (c) represented by formula (1) using a catalyst (d) such as a Lewis acid catalyst. It is produced by polymerization. Usually, since (meth)acrylic acid ester compounds are not cationic polymerizable, they do not copolymerize with vinyl aromatic compounds. However, when a (meth)acrylic acid ester compound is an ester with a secondary or tertiary alcohol, in the presence of an acid catalyst such as a Lewis acid catalyst, secondary or tertiary carbon is cleaved and secondary or tertiary carbon is cleaved. Generates positive ions and (meth)acrylic acid anions. Then, polymerization is initiated from secondary or tertiary carbocations. However, this initiation reaction does not necessarily have high initiator efficiency, and it is presumed that a part of the initiator is discharged to the outside of the system as an alkane such as butane. In addition, (meth)acrylic acid units are introduced into the stationary terminals by recombination with the (meth)acrylic acid anion generated by the initiation reaction with the terminal carbocation as an active species.

As described above, the terminal groups derived from the (meth)acrylic acid ester compound (c) include the terminal groups represented by the formulas (2) and (3), and the terminal groups represented by the formula (2) are secondary or tertiary. Although it consists of an alkyl group, it is thought that the amount of the terminal group (c1) in the formula (3) is somewhat smaller than the amount of the terminal group (c1) in the formula (3) because this part is discharged out of the system concurrently with a reaction in which an alkane is formed. . Therefore, it can be said that it is good to specify the amount of end groups by the amount of end groups (c1).

The amount of divinyl aromatic compound (a) and monovinyl aromatic compound (b) used is 5 to 95 mol% of divinyl aromatic compound (a) and 95 to 5 mol of monovinyl aromatic compound (b), based on 100 mol% of both in total. %, preferably 15 to 70 mol% of the divinyl aromatic compound (a) and 85 to 30 mol% of the monovinyl aromatic compound (b).

The divinyl aromatic compound (a) plays an important role as a cross-linking component for branching and polyfunctionalizing the copolymer, as well as for expressing heat resistance when the copolymer is thermally cured. As examples of the divinyl aromatic compound (a), divinylbenzene (including each isomer), divinylnaphthalene (including each isomer), and divinylbiphenyl (including each isomer) are preferably used, but are limited to these. it is not going to be In addition, these can be used individually or in combination of 2 or more types. From the viewpoints of molding processability and heat discoloration resistance, divinylbenzene (m-isomer, p-isomer or a mixture of these isomers) is more preferable.

The monovinyl aromatic compound (b) improves the solvent solubility and processability of the copolymer. Examples of the monovinyl aromatic compound (b) include, but are not limited to, styrene, nucleus alkyl-substituted monovinyl aromatic compounds, α-alkyl-substituted monovinyl aromatic compounds, β-alkyl-substituted styrene, and alkoxy-substituted styrene. In order to prevent gelation of the copolymer and to improve solubility and processability in solvents, styrene, ethylvinylbenzene (including each isomer) and ethylvinylbiphenyl (including each isomer) are particularly effective due to cost and ease of availability. It is preferably used from the point of view. From the viewpoint of dielectric properties, more preferred is ethylvinylbenzene (m-isomer, p-isomer or a mixture of these isomers).

Further, in addition to the divinyl aromatic compound (a) and the monovinyl aromatic compound (b), a trivinyl aromatic compound, a trivinyl aliphatic compound, or a divinyl aliphatic compound, within a range that does not impair the effects of the present invention during the production of the copolymer. and other monomers (e) such as monovinyl aliphatic compounds, and these units can be introduced into the copolymer.

Specific examples of the other monomer (e) include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diacrylate, and butadiene. However, it is not limited thereto. These can be used individually or in combination of 2 or more types. Other monomers (e) are preferably used within the range of less than 30 mol% of the total monomers. Thereby, the structural unit derived from the other monomer component (e) is within the range of less than 30 mol% with respect to the total amount of structural units in the copolymer. In addition, when referring to all monomers, a (meth)acrylic acid ester compound (c) is included in addition to monomers having a polymerizable double bond such as divinyl aromatic compound (a) and monovinyl aromatic compound (b).

The (meth)acrylic acid ester compound (c) is represented by the above formula (1), which causes a cleavage reaction with the catalyst (d) during the initiation reaction to produce polymerization active species composed of secondary or tertiary carbocations. In addition, the (meth)acrylic acid anion generated by the initiation reaction recombines with the terminal carbocation, which is a polymerization active species, as a chain transfer agent, thereby imparting functions such as toughness, low light transmission loss, and processability to the terminal of the copolymer. make it possible

The terminal groups generated from the (meth)acrylic acid ester compound (c) are represented by formulas (2) and (3), and are thought to bond to the initiating and terminal ends of the copolymer, respectively.

The (meth)acrylic acid ester compound (c) is one type of monomer as described above, but is also a polymerization additive. This is also a chain transfer agent because it imparts the above terminal group (which is one of the structural units) to the copolymer by a chain transfer reaction.

As the (meth)acrylic acid ester compound (c), t-butyl methacrylate, sec-butyl methacrylate, t-butyl acrylate or sec-butyl acrylate is preferable from the viewpoints of reactivity, availability, and heat resistance of the cured product. used From the viewpoint of reaction rate, t-butyl methacrylate or t-butyl acrylate is more preferably used.

The amount of the (meth)acrylic acid ester compound (c) used is preferably 0.5 to 300 moles, preferably 1 to 200 moles, based on the total of 100 moles of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b). More preferably, it is 10-150 mol. If the amount used is too small, the amount of introduction of the terminal groups is reduced, resulting in deterioration in functions such as toughness, as well as an increase in molecular weight and molecular weight distribution, resulting in deterioration in molding processability. Moreover, when it is too large, the polymerization rate is markedly lowered, the productivity is lowered, and the refractive index is lowered. During the polymerization reaction, the (meth)acrylic acid ester compound (c) reacts with the catalyst (d) to initiate the polymerization reaction and also forms the terminal group to stop the growth. The usage amount and reaction conditions are selected so that the introduction amount of the terminal group derived from the (meth)acrylic acid ester compound (c) is within the range specified in the description of the copolymer.

The polymerization reaction uses a divinyl aromatic compound (a), a monovinyl aromatic compound (b), a (meth)acrylic acid ester compound (c), and a catalyst (d), and the polymerization raw materials including these compounds have a dielectric constant of 2.0 to 2.0. It is preferable to obtain a terminal-modified copolymer by cationic copolymerization at a temperature of 20 to 120 ° C in a homogeneous solvent dissolved in a 15.0 solvent.

As the catalyst (d), at least one selected from the group consisting of Lewis acid catalysts, inorganic strong acids and organic sulfonic acids is used.

The Lewis acid catalyst is a compound composed of a metal ion (acid) and a ligand (base), and any compound capable of accepting an electron pair can be used without particular limitation. Among the Lewis acid catalysts, from the viewpoint of the thermal decomposition resistance of the resulting copolymer, particularly divalent to hexavalent metals such as B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Ti, W, Zn, Fe, and V Fluorides are preferred. Moreover, sulfuric acid, hydrochloric acid, phosphoric acid, etc. are mentioned as an inorganic strong 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 control of the molecular weight and molecular weight distribution of the resulting copolymer and polymerization activity, boron trifluoride ether (diethyl ether, dimethyl ether, etc.) complexes are most preferably used.

The catalyst (d) is preferably used within the range of 0.001 to 10 moles per mole of the (meth)acrylic acid ester compound (c), but is more preferably 0.001 to 1 mole. If it exceeds 10 moles, the polymerization rate becomes excessively high, making it difficult to control the molecular weight distribution and reducing the amount of terminal groups derived from compound (c) introduced.

Esters obtained from primary alcohols such as ethyl acetate, n-propyl acetate, and n-butyl acetate and carboxylic acids (excluding (meth)acrylic acid) as desired in the production of terminal-modified soluble polyfunctional vinyl aromatic copolymers Compounds, or at least one compound selected from dialkyl ketones having 1 to 30 carbon atoms such as methyl ethyl ketone and methyl isobutyl ketone can be used as the cocatalyst (f). The amount of the cocatalyst (f) used is less than 300 moles, preferably less than 200 moles, and more preferably less than 150 moles, based on 100 moles of the total of the divinyl aromatic compound (a) and the monovinyl aromatic compound (b). The cocatalyst is effective for increasing the selectivity of the reaction and controlling the molecular weight by interacting with the active species or catalyst (d) during the polymerization reaction, but when used in excess, the polymerization rate is remarkably lowered and the yield of the copolymer decreases do.

This polymerization reaction is preferably carried out in at least one organic solvent having a dielectric constant of 2 to 15 as a solvent for dissolving the resulting terminal-modified soluble polyfunctional vinyl aromatic copolymer. The organic solvent is a compound that does not inherently inhibit cationic polymerization, and dissolves the catalyst, polymerization additive, cocatalyst, monomer, and polyfunctional vinyl aromatic copolymer to form a homogeneous solution, as long as the dielectric constant is within the range of 2 to 15. There is no restriction|limiting in particular, It can use individually or in combination of 2 or more types. When the permittivity of the solvent is low, the molecular weight distribution is widened, and when the permittivity of the solvent is high, the polymerization rate is lowered.

As the organic solvent, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane are preferable from the viewpoint of polymerization activity and solubility balance. In addition, considering the viscosity of the obtained polymerization solution and ease of heat removal, the concentration of the copolymer in the polymerization solution at the end of the polymerization is 1 to 90 wt%, preferably 10 to 80 wt%, particularly preferably 20 to 70 wt%. % is determined to be When this concentration is less than 1 wt%, cost increases due to low polymerization efficiency, and when 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 to 120°C, preferably 40 to 100°C. If the polymerization temperature is too high, the selectivity of the reaction is lowered, resulting in problems such as an increase in molecular weight distribution or the generation of gels.

After the polymerization reaction is stopped, the method for recovering the copolymer is not particularly limited, and a commonly used method such as steam stripping or precipitation in a poor solvent may be used.

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

Next, the first aspect of the curable composition of the present invention will be described. The curable composition according to this first aspect is useful as a substrate material in the field of advanced electronic devices, for example, as an electrical insulating material or a material for laminates.

The curable composition according to the first aspect contains a terminal 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 is cured by causing a crosslinking reaction by means such as heating as described later, but the reaction temperature at that time is lowered or the crosslinking reaction of the unsaturated group is promoted. For this purpose, a radical polymerization initiator (XB) may be contained and used. The amount of the radical polymerization initiator used for this purpose is 0.01 to 10% by weight, preferably 0.1 to 8% by weight based on the sum of components (XA) and (XB). Since the radical polymerization initiator is a radical polymerization catalyst, it is represented by a radical polymerization initiator below.

A known substance is used as the radical polymerization initiator. Representative examples include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne- 3, di-t-butyl peroxide, t-butylcumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t -Butylperoxy)hexane, dicumylperoxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t -Peroxides such as butyl peroxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, and trimethylsilyltriphenylsilylperoxide, but are not limited thereto . In addition, although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane 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.

When the blending amount of the radical polymerization initiator is in the range of 0.01 to 10 parts by weight with respect to the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA), the reaction proceeds satisfactorily without inhibiting the curing reaction.

Further, even if the curable composition containing the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) is cured by blending, if necessary, another polymerizable monomer copolymerizable with the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention. good night.

As the polymerizable monomer capable of copolymerization, known substances are used. Representative examples include styrene, styrene dimer, alphamethylstyrene, alphamethylstyrenedimer, divinylbenzene, vinyltoluene, t-butylstyrene, chlorostyrene, dibromostyrene, vinylnaphthalene, vinylbiphenyl, acenaphthylene, Divinyl benzyl ether, allyl phenyl ether, etc. are mentioned.

In addition, the curable composition containing the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention includes a known thermosetting resin, such as a vinyl ester resin, polyvinylbenzyl resin, an unsaturated polyester resin, a curable vinyl resin, a modified polyphenylene ether resins, maleimide resins, epoxy resins, polycyanate resins, phenol resins, etc., known thermoplastic resins such as polystyrene, polyphenylene ether, polyetherimide, polyethersulfone, PPS resin, poly cyclopentadiene resins, polycycloolefin resins, etc., or known thermoplastic elastomers such as styrene-ethylene-propylene copolymers, styrene-ethylene-butylene copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, It is also possible to blend with hydrogenated styrene-butadiene copolymers, hydrogenated styrene-isoprene copolymers, etc., or rubbers such as polybutadiene and polyisoprene.

The curable composition of the present invention is a modified polyphenylene ether (XC) represented by the following formula (7) in a curable composition containing a terminal modified soluble polyfunctional vinyl aromatic copolymer (XA) and a radical polymerization initiator (XB), particularly Modified polyphenylene ether (XC) having a group having at least one polymerizable unsaturated double bond at the terminal, for example, a phenolic hydroxyl group, a vinyl group, or a (meth)acrylic group, may be contained. The terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) and the modified polyphenylene ether (XC) of the present invention have good compatibility, and overcome the problem of a decrease in reliability due to a decrease in compatibility, and can be mixed at any time. As a result, it exhibits improved properties such as high-level low dielectric properties and toughness, formability and interlayer peel strength.

In 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, a group represented by 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. T represents a hydrogen atom when m is 1, and represents an alkylene group, a group represented by the following formula (10) or (11) when m is 2.

In formula (8), n represents a positive integer of 50 or less, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, An alkenylcarbonyl group or an alkynylcarbonyl group is shown.

In formula (9), X is an organic group having 1 or more carbon atoms and may contain an oxygen atom. Y is a vinyl group. 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 formyl 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 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, or an alkylcarbonyl group , an alkenylcarbonyl group, or an alkynylcarbonyl group. F is a straight-chain, branched or cyclic hydrocarbon group having 20 or less carbon atoms, including 0 carbon atoms.

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

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

Moreover, M represents the group represented by a hydrogen atom and Formula (9). In addition, M is not a hydrogen atom when m is 1, that is, when modified polyphenylene ether is T-L-M, but represents a group represented by formula (9). In addition, M is when m is 2, that is, when the modified polyphenylene ether is M-L-T-L-M, at least one of the two Ms is not a hydrogen atom, and for the reason of heat resistance and toughness of the cured product, both Ms are represented by the formula (9) A group represented by is preferred.

In addition, T represents a hydrogen atom when m is 1, that is, when modified polyphenylene ether is T-L-M. The modified polyphenylene ether represented by T-L-M is a modified polyphenylene ether represented by H-L-M. In addition, T represents an alkylene group, a group represented by formula (10), or a group represented by formula (11) when m is 2, that is, when modified polyphenylene ether is M-L-T-L-M. Among these, it is preferable that m is 2 and T is an alkylene group, and it is preferable that m is 2 and T is a 2,2-propylene group from the viewpoint of the toughness of the cured product and the solubility of modified polyphenylene ether.

In Formula (10), R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. indicates R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ may be the same group or different groups.

In R ⁵ to R ²¹ , specific examples of the enumerated functional groups include the following.

Although the alkyl group is not particularly limited, for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specifically, a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group etc. are mentioned.

In addition, the alkenyl group is not particularly limited, but, for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Specifically, a vinyl group, an allyl group, and a 3-butenyl group etc. are mentioned.

Also, the alkynyl group is not particularly limited, but, for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specifically, an ethynyl group, a prop-2-yn-1-yl group (propargyl group), etc. are mentioned, for example.

Further, the alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, but, for example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable. An acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, and a cyclohexylcarbonyl group etc. are mentioned specifically,.

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 preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable. Specifically, an acryloyl group, a methacryloyl group, and a crotonoyl group etc. are mentioned, for example.

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 preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable. Specifically, a propioloyl group etc. are mentioned, for example.

The number average molecular weight of the modified polyphenylene ether is not particularly limited, but is preferably from 800 to 7000, and more preferably from 1000 to 5000. It is most preferable that it is 1000-3000. 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 numerical value within this range. Specifically, it is preferably 1 to 50. In addition, here, the number average molecular weight should just be measured by a general molecular weight measuring method, and the value measured using gel permeation chromatography (GPC) specifically, etc. are mentioned.

When the number average molecular weight of the modified polyphenylene ether is within this range, the toughness and moldability of the cured product of the obtained curable composition will be higher. This is because the modified polyphenylene ether has a relatively low molecular weight when the number average molecular weight is within this range, so the fluidity is improved while maintaining toughness. In normal polyphenylene ether, when such a low molecular weight is used, the heat resistance and toughness of the cured product tend to decrease. However, since the modified polyphenylene ether used in the present embodiment has a polymerizable unsaturated double bond at its terminal, it is cured together with a vinyl-based thermally crosslinkable curable resin to crosslink the modified polyphenylene ether and the thermally crosslinkable curable resin. proceeds favorably, and a cured product having sufficiently high heat resistance and toughness is obtained. Therefore, the hardened|cured material of the obtained curable composition can obtain what is excellent in both heat resistance and toughness.

The curable composition of the present invention is an epoxy resin (XD) and a curing agent ( A curable composition characterized by containing XE) is also a preferred embodiment.

There is no particular restriction on the epoxy resin as component (XD), but examples of the epoxy resin include an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, an epoxy resin having two or more epoxy groups and a cyanurate structure in one molecule, and/or It is preferable to use one or more types of epoxy resins selected from the group consisting of epoxy resins having two or more epoxy groups and an alicyclic structure in one molecule. As the component (XD), bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkylphenol novolak type epoxy resin, xylylene-modified phenol novolak type epoxy resin, xylylene-modified alkylphenol novolac 1 type selected from the group consisting of type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, triglycidyl isocyanurate, cyclohexane type epoxy resin and adamantane type epoxy resin It is more preferable that it is the above epoxy resin.

(XD) As a bisphenol F-type epoxy resin used as a component, for example, an epoxy resin containing diglycidyl ether of 4,4'-methylene bis (2,6-dimethylphenol) as a main component, 4,4'-methylene An epoxy resin containing diglycidyl ether of bis(2,3,6-trimethylphenol) as a main component, and an epoxy resin containing diglycidyl ether of 4,4'-methylenebisphenol as a main component are exemplified. Among them, an epoxy resin containing diglycidyl ether of 4,4'-methylenebis(2,6-dimethylphenol) as a main component is preferred. As said bisphenol F-type epoxy resin, it can obtain as a commercial item as Nippon-Steel Sumikin Chemical Co., Ltd. brand name YSLV-80XY.

Examples of the biphenyl type epoxy resin include epoxy resins such as 4,4'-diglycidyl biphenyl and 4,4'-diglycidyl-3,3',5,5'-tetramethyl biphenyl. . As said biphenyl type epoxy resin, it can obtain as a commercial item as Mitsubishi Chemical Corporation brand name YX-4000, YL-6121H.

Dicyclopentadiene type epoxy resins include dicyclopentadiene dioxide and phenol novolak epoxy monomers having a dicyclopentadiene skeleton.

Examples of the naphthalene type epoxy resin include 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, and 2,7-diglycidylnaphthalene. Glycidylnaphthalene, triglycidylnaphthalene, and 1,2,5,6-tetraglycidylnaphthalene, naphthol/aralkyl type epoxy resins, naphthalene skeleton modified cresol novolak type epoxy resins, methoxynaphthalene modified cresol novolak type Modified naphthalene type epoxy resins, such as an epoxy resin, a naphthylene ether type epoxy resin, and a methoxy naphthalene dimethylene type epoxy resin, etc. are mentioned.

Further, as adamantane type epoxy resins, 1-(2,4-diglycidyloxyphenyl)adamantane, 1-(2,3,4-triglycidyloxyphenyl)adamantane, and 1,3-bis (2,4-diglycidyloxyphenyl)adamantane, 1,3-bis(2,3,4-triglycidyloxyphenyl)adamantane, 2,2-bis(2,4-diglycidyl) Cidyloxyphenyl) 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; and the like.

Bisphenol F-type epoxy resin, alkylphenol novolac-type epoxy resin, xylylene-modified phenol novolak-type epoxy resin from the viewpoint of compatibility with component (XA), dielectric properties, and small warpage of molded products among the above epoxy resins , xylylene-modified alkylphenol novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, triglycidyl isocyanurate, cyclohexane type epoxy resin, adamantene type epoxy Resin is preferably used.

(XD) It is preferable that the weight average molecular weight (Mw) of the epoxy resin used as a component is less than 10,000. More preferably Mw is 600 or less, More preferably, it is 200 or more and 550 or less. When the Mw is less than 200, the volatility of this component tends to increase and the handling properties of the cast film/sheet tend to deteriorate. On the other hand, when Mw exceeds 10,000, the cast film sheet is hard and brittle, and the adhesiveness of the cured product of the cast film sheet tends to decrease.

The content of component (XD) preferably has a lower limit of 5 parts by weight and an upper limit of 100 parts by weight with respect to 100 parts by weight of component (XA). More preferably, the lower limit of the content of component (XD) is 10 parts by weight relative to 100 parts by weight of component (XA). On the other hand, a more preferable upper limit is 80 parts by weight, and a still more preferable upper limit is 60 parts by weight. When the content of component (XD) satisfies the above preferable lower limit, the adhesiveness of the cured product of the cast film/sheet can be further improved. When the content of component (XD) satisfies the above preferable upper limit, the handleability of the cast film/sheet in an uncured state is further enhanced, the adhesion to the glass cloth is improved, and the reliability is increased.

The curing agent of component (XE) is a phenolic resin, 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 group-terminated polyphenylene ether oligomer, and an active ester compound. it is desirable By using these preferable curing agents, a curable composition that becomes a cured product having an excellent balance of heat resistance, moisture resistance and dielectric properties can be obtained.

The phenol resin used as a curing agent for component (XE) is not particularly limited. Specific examples of the phenolic resin include phenol novolac, o-cresol novolac, p-cresol novolac, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type novolak, phenol aralkyl resin , naphthol aralkyl resin, biphenyl type phenol novolac resin, biphenyl type naphthol novolac resin, decalin modified novolac, poly(di-o-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane , and poly(di-p-hydroxyphenyl)methane. Among them, a phenol resin having a melamine skeleton, a phenol resin having a triazine skeleton, or a phenol resin having an allyl group are preferred because the flexibility and flame retardancy of the insulating sheet can be further improved.

Examples of commercially available products of the phenolic resin include MEH-8005, MEH-8010 and NEH-8015 (all of which are manufactured by Maywa Kasei Co., Ltd.), YLH903 (available from Japan Epoxy Resin Co., Ltd.), LA-7052, LA-7054, LA-7751, and LA-1356. and LA-3018-50P (manufactured by DIC Corporation), and PS6313 and PS6492 (manufactured by Gunsakae Chemical Co., Ltd.).

The structure is not particularly limited also for the acid anhydride having an aromatic skeleton used as a curing agent for component (XE), a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride. As an acid anhydride having an aromatic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride, for example, styrene/maleic anhydride copolymer, benzophenone tetracarboxylic acid anhydride, pyromellitic anhydride, trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenylethynylphthalic anhydride, glycerol bis(anhydrotrimeritate) monoacetate, ethylene glycol bis(anhydrotrimeritate), methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and trialkyltetrahydrophthalic anhydride, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, or an acid anhydride having a dicyclopentadiene skeleton, or a modified product of the acid anhydride.

Examples of commercially available acid anhydrides having an aromatic backbone, 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 (all of which are manufactured by Sartomer Japan Co., Ltd.), ODPA-M And PEPA (all of the above are manufactured by Manark), Rikkagit MTA-10, Rikkagit MTA-15, Rikkagit TMTA, Rikkagit TMEG-100, Rikkagit TMEG-200, Rikkagit TMEG-300, Rikkagit TMEG-500, Recagit TMEG-S, Recagit TH, Recagit HT-1A, Recagit HH, Recagit MH-700, Recagit MT-500, Recagit DSDA, and Recagit TDA-100 (all of the above are manufactured by Nippon Chemical Co., Ltd.), and EPICLON B4400, EPICLON B650, and EPICLON B570 (all of which are manufactured by DIC Corporation).

The acid anhydride having an alicyclic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride is an acid anhydride having a polyalicyclic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride, or a terpene-based compound. An acid anhydride having an alicyclic skeleton obtained by addition reaction of maleic anhydride, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride is preferable. In this case, the flexibility, moisture resistance or adhesiveness of the insulating sheet can be further improved. Further, as the acid anhydride having an alicyclic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride, there may be mentioned methylnadic acid anhydride, an acid anhydride having a dicyclopentadiene skeleton, or a modified product of the acid anhydride. .

Examples of commercially available acid anhydrides having an alicyclic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride include Rikagit HNA and Rikagit HNA-100 (all of which are manufactured by Nippon Chemical Co., Ltd.), Epicur YH306 and Epicure YH307. , Epicure YH308H and Epicure YH309 (all of which are manufactured by Japan Epoxy Resin Co., Ltd.).

(XE) As a component, a hydroxyl terminal polyphenylene ether oligomer can also be used. Hydroxyl terminal polyphenylene ether oligomer represented by following formula (12) is mentioned.

In 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. V represents a hydrogen atom when p is 1, and represents an alkylene group, a group represented by the following formula (14) or formula (15) when p is 2.

In formula (13), q represents a positive integer of 50 or less, and R ²² , R ²³ , R ²⁴ , and R ²⁵ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, An alkenylcarbonyl group or an alkynylcarbonyl group is shown.

(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 formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. .)

In formula (15), R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, or an alkylcarbonyl group , an alkenylcarbonyl group, or an alkynylcarbonyl group. F is a straight-chain, branched or cyclic hydrocarbon group having 20 or less carbon atoms, including 0 carbon atoms.

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

As the active ester compound used as component (XE), from the viewpoint of heat resistance, etc., an active ester compound obtained by reacting a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound is preferable. , An active ester compound 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 is more preferable, and in the present invention, a carboxylic acid compound and An aromatic compound obtained by reacting an aromatic compound having a phenolic hydroxyl group and having at least two active ester groups in the molecule is particularly preferred. The active ester compound used as component (XE) may be linear or multi-branched, and in the case where the active ester compound is derived from a compound having at least two carboxylic acids in a molecule, such at least two carboxylic acids When the compound contained in the molecule contains an aliphatic chain, compatibility with the epoxy resin can be increased, and when it has an aromatic ring, heat resistance can be increased.

Specific examples of the carboxylic acid compound for forming the active ester compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among these, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, phthalic acid, isophthalic acid, and terephthalic acid are more preferable, and isophthalic acid and terephthalic acid are still more preferable.

Specific examples of the thiocarboxylic acid compound for forming the active ester compound include thioacetic acid and thiobenzoic acid.

Specific examples of the phenol compound and naphthol compound for forming the active ester compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxy hydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac and the like. Among these, from the viewpoint of heat resistance and solubility, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, and tetrahydroxy Benzophenone, dicyclopentadienyldiphenol, and phenol novolac are preferred, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and phenol novolak are more preferred, Dicyclopentadienyldiphenol and phenol novolac are more preferred.

Specific examples of the thiol compound for forming the active ester compound include benzenedithiol and triazinedithiol.

As an active ester compound, the active ester compound disclosed in Unexamined-Japanese-Patent No. 2002-12650 and Unexamined-Japanese-Patent No. 2004-277460, or a commercially available thing can be used, for example. As a commercially available active ester compound, for example, brand name "EXB9451, EXB9460, EXB9460S, HPC-8000-65T" (above, made by DIC Corporation), brand name "DC808" (made by Japan Epoxy Resin Co., Ltd.), brand name "YLH1026" (Japan Epoxy) resin company) etc. are mentioned.

The method for producing the active ester compound is not particularly limited, and can be produced by a known method. For example, a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound can be obtained by

The compounding amount of the active ester compound (XE) in the curable composition of the present invention is preferably 20 to 120 parts by weight, more preferably 40 to 100 parts by weight, and still more preferably based on 100 parts by weight of the epoxy resin (XD). It is in the range of 50 to 90 parts by weight. By setting the blending amount of the active ester compound (XE) within the above range, the dielectric properties, heat resistance and coefficient of linear expansion as a cured product can be improved.

As the curing agent used as component (XE), o-cresol novolac, p-cresol novolac, t-butylphenol novolac, dicyclopentadiene from the viewpoint of compatibility with the component (XA) of the present invention, moisture resistance and adhesiveness Cresol, polyparavinylphenol, xylylene-modified novolac, poly(di-o-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane, poly(di-p-hydroxyphenyl)methane, It is preferably selected from methylnadic anhydride, trialkyltetrahydrophthalic anhydride, an acid anhydride having a dicyclopentadiene skeleton or a modified product of the acid anhydride, a hydroxyl group-terminated polyphenylene ether oligomer, or an active ester compound.

The curable composition comprising the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention has inorganic fillers such as fused silica, crystalline silica, alumina, silicon nitride and aluminum nitride, flame retardancy such as decabromodiphenylethane and brominated polystyrene. By using the imparting agent in combination, it can be used particularly usefully as an electric or electronic component material requiring dielectric properties, flame retardancy or heat resistance, in particular, a semiconductor sealing material or a varnish for a circuit board.

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

A cured product obtained by curing a curable composition containing the terminal-modified soluble polyfunctional vinyl aromatic copolymer (XA) of the present invention can be used as a molded product, laminate, molded product, adhesive, coating film, or film. For example, the cured product of the semiconductor sealing material is a molded product or a molded product, and as a method of obtaining a cured product for this purpose, the compound is molded using a mold or a transfer molding machine, an injection molding machine, etc. A cured product can be obtained by heating for 0.5 to 10 hours. In addition, the cured product of the varnish for circuit board is a laminate, and as a method of obtaining this cured product, the varnish for circuit board is impregnated into a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper. It heat-drys and obtains a prepreg, and it can obtain by hot-press-molding by laminating|stacking it individually or with metal foil, such as copper foil.

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

In addition, the curable composition of the present invention can be used by being bonded to a metal foil (meaning including a metal plate. Hereinafter, the same applies) similarly to a cured composite material described later.

Next, the curable composite material of the curable composition of the present invention and its cured product will be described. A substrate is added to the curable composite material of the curable composition of the present invention in order to increase mechanical strength and increase dimensional stability.

Known materials are used as such substrates, but examples include various glass cloths such as rubbing cloths, cloths, chopped mats, and surfacing mats, asbestos cloths, metal fiber cloths and other synthetic or natural inorganic fiber cloths, and wholly aromatic polyamides. Woven or non-woven fabrics obtained from liquid crystal fibers such as fibers, wholly aromatic polyester fibers and polybenzoxal fibers, woven or non-woven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, and acrylic fibers, cotton fabrics, hemp cloths, felts, etc. Fabrics such as natural cellulose fabrics such as natural fiber fabrics, carbon fiber fabrics, kraft paper, cotton paper, and paper-glass blended paper, papers, etc. may be used alone or in combination of two or more.

The proportion of the base material in the curable composite material is preferably 5 to 90 wt%, preferably 10 to 80 wt%, and more preferably 20 to 70 wt%. When the amount of the base material is less than 5 wt%, the composite material has insufficient dimensional stability and strength after curing, and when the amount of the base material exceeds 90 wt%, the dielectric properties of the composite material deteriorate, which is undesirable.

A coupling agent may be used in the curable composite material of the present invention for the purpose of improving adhesion at the interface between the resin and the substrate, if necessary. As the coupling agent, common ones such as silane coupling agents, titanate coupling agents, aluminum-based coupling agents, and dilcoaluminate coupling agents can be used.

As a method for producing the curable composite material of the present invention, for example, the curable composition of the present invention and other components, if necessary, are uniformly dissolved or dispersed in the above-mentioned aromatic solvent, ketone solvent, etc., or a mixed solvent thereof, and then impregnated. , a method of drying. Impregnation is performed by dipping (dipping), application, or the like. Impregnation can be repeated a plurality of times as necessary, and at this time, it is also possible to repeat impregnation using a plurality of solutions having different compositions or concentrations, and finally adjust the desired resin composition and resin amount.

A curable composite material is obtained by curing the curable composite material of the present invention by a method such as heating. The manufacturing method is not particularly limited. For example, a curable composite material having a desired thickness can be obtained by stacking a plurality of curable composite materials, bonding the layers together under heat and pressure, and performing thermal curing. It is also possible to obtain a new layered cured composite material by combining a curable composite material and a curable composite material that have been bonded and cured once. Lamination molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed alone. That is, an uncured or semi-cured composite material obtained by pre-lamination molding can be cured by treating with heat treatment or other methods.

Molding and curing are temperature: 80 to 300 ° C, pressure: 0.1 to 1000 kg / cm 2, time: 1 minute to 10 hours, more preferably temperature: 150 to 250 ° C, pressure 1 to 500 kg / cm 2, time: 1 It can be performed in the range of minutes to 5 hours.

The laminate of the present invention is composed of a layer of the cured composite material of the present invention and a layer of metal foil. As a metal foil used here, copper foil, aluminum foil, etc. are mentioned, for example. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 3 to 105 μm.

As a method for producing the laminate of the present invention, for example, the curable composite material obtained from the curable composition of the present invention described above and the base material, and metal foil are laminated in a layer configuration according to the purpose, and each layer is bonded under heating and pressurization, and at the same time, heat curing There are ways to get angry. In the laminate of the curable composition of the present invention, the cured composite material and the metal foil are laminated in an arbitrary layer configuration. Metal foil can be used both as a surface layer and as an intermediate layer. In addition to the above, it is also possible to form multiple layers by repeating lamination and curing a plurality of times.

An adhesive may be used for adhesion to the metal foil. Examples of the adhesive include epoxy, acrylic, phenol, and cyanoacrylate adhesives, but are not particularly limited thereto. The laminate molding and curing may be performed under the same conditions as those of the cured composite material of the present invention.

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

The method for producing the film of the present invention is not particularly limited, and for example, the curable composition and other components as necessary are uniformly dissolved or dispersed in an aromatic or ketone-based solvent or a mixed solvent thereof to obtain a PET film or the like. The method of drying after apply|coating to a resin film, etc. are mentioned. It is also possible to repeat the application a plurality of times as necessary, and at this time, it is also possible to repeat the application using a plurality of solutions having different compositions or concentrations, and finally adjust the desired resin composition and resin amount.

The metal foil with resin of this invention is comprised from the curable composition of this invention and metal foil. As a metal foil used here, copper foil, aluminum foil, etc. are mentioned, for example. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.

The method for producing the resin-coated metal foil of the present invention is not particularly limited. For example, the curable composition and other components as necessary are uniformly dissolved or dispersed in an aromatic solvent, a ketone solvent, or a mixed solvent thereof to form a metal foil. A method of drying after application may be mentioned. It is also possible to repeat the application a plurality of times as necessary, and at this time, it is also possible to repeat the application using a plurality of solutions having different compositions and concentrations, and finally adjust to the desired resin composition and resin amount.

The terminal-modified soluble polyfunctional vinyl aromatic copolymer of the present invention can be processed into molding materials, sheets, or films, and can satisfy characteristics such as low permittivity, low water absorption, and high heat resistance in fields such as the electric industry, aerospace and aerospace industries. It can be used for low-k dielectric materials, insulating materials, heat-resistant materials, structural materials, etc. In particular, it can be used as single-sided, double-sided, multilayer printed boards, flexible printed boards, build-up boards, and the like. In addition, semiconductor-related materials or optical materials, paints, photosensitive materials, adhesives, sewage treatment agents, heavy metal collectors, ion exchange resins, antistatic agents, antioxidants, antifogging agents, rust inhibitors, flame retardants, disinfectants, insect repellents, medical materials, It can be applied to coagulants, surfactants, lubricants, binders for solid fuels, and conductive treatment agents.

In addition, the curable composition of the present invention provides a cured product having high dielectric properties (low dielectric constant and low dielectric loss tangent) even after severe heat history, and high adhesion reliability even under severe environments, and excellent resin fluidity. , low linear expansion, and excellent wire embedding flatness. Therefore, in fields such as the electric/electronic industry, space/aircraft industry, etc., in response to the recent strong demand for miniaturization and ultra-thinning as dielectric materials, insulating materials, heat-resistant materials, structural materials, etc., molding defects such as warping have occurred. It is possible to provide a cured molded article without In addition, a resin composition, a cured product, or a material containing the resin composition and a cured product having excellent reliability due to excellent wiring embedding flatness and excellent adhesion between different materials can be realized.

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

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

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

Next, the component (B) in the curable resin composition according to the second aspect will be described.

Component (B) is at least one vinyl compound having at least one unsaturated group in the molecule. And component (B) is not the same as component (A). That is, (A) component is not handled as (B) component.

Here, the vinyl compound may be a 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 plural. Hereinafter, the unsaturated group is also referred to as a vinyl group. (B) The vinyl group of component (A) is copolymerizable with the vinyl group which component has.

As a preferable component (B), there is one or more types of (meth)acrylates having one or more (meth)acryloyl groups in the molecule. In addition, there are at least one (meth)acrylate having a hydroxyl group and/or a carboxyl group.

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

Examples of the (meth)acrylate compound having one (meth)acryloyl group in the molecule include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. , butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, butoxyethyl (meth)acrylate, pentyl (meth)acrylate, Hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth) Acrylates, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate , Behenyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate aliphatic (meth)acrylates such as; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate Alicyclic (meth)acrylates, such as a rate; Phenyl (meth)acrylate, benzyl (meth)acrylate, o-biphenyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, phenoxyethyl (meth)acrylate Acrylate, p-cumylphenoxyethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, 1-naphthoxyethyl (meth)acrylate, 2-naphthoxyethyl (meth)acrylate, phenoxy aromatic (meth)acrylates such as oxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, and phenoxypolypropylene glycol (meth)acrylate; Heterocyclics such as 2-tetrahydrofurfuryl (meth)acrylate, N-(meth)acryloyloxyethylhexahydrophthalimide, and 2-(meth)acryloyloxyethyl-N-carbazole (meth) Acrylates etc. are mentioned.

In addition, examples of the polyfunctional (meth)acrylate having two or more (meth)acryloyl groups in the molecule include 1,4-butanedioldi(meth)acrylate and 1,6-hexanedioldi(meth)acrylate. , 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, bisphenol A polyethoxydi(meth)acrylate, bisphenol A polypropoxydi(meth)acrylate, bisphenol F Polyethoxydi(meth)acrylate, Ethylene glycol di(meth)acrylate, Trimethylolpropanetrioxyethyl(meth)acrylate, Tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate rate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, hydro Neophene glycol di(meth)acrylate oxybivalate, di(meth)acrylate of ε-caprolactone adduct of neophene glycol hydroxybivalate (e.g., manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX- 220, HX-620, etc.), trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate, and dimethylolpropane tetra(meth)acrylate. there is.

Among these, from the viewpoint of transparency and heat resistance, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( aliphatic (meth)acrylates such as meth)acrylate; alicyclic (meth)acrylate; aromatic (meth)acrylates; It is preferable that it is a heterocyclic (meth)acrylate.

These compounds can be used individually or in combination of 2 or more types.

When the curable resin composition of the present invention is used as a curable resin composition for forming an optical waveguide, the component (B) is a vinyl compound having a structural unit represented by the general formula (16) or (17), or generated from the vinyl compound. It is preferable to include a curable vinyl-based polymer that does.

In 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 , X ² is a divalent organic group having 1 to 20 carbon atoms which may contain a single bond or at least one bond selected from the group consisting of ester bond, ether bond, thioester bond, thioether bond and amide bond; indicate

It is preferable that the vinyl compound having the structural unit represented by the general formula (16) or (17) or the curable vinyl polymer generated from the vinyl compound is a (meth)acrylate or a (meth)acrylate polymer.

Here, the curable vinyl polymer may be obtained by homopolymerization or copolymerization of the above vinyl compound, and may have at least one vinyl group.

In the general formula (16) or (17), when X ¹ and X ² are divalent organic groups having 1 to 20 carbon atoms, there is no particular limitation as the divalent organic group, and examples include an alkylene group, a cycloalkylene group, and a phenyl group. divalent organic groups including a ene group, a biphenylene group, a polyether group, a polysiloxane group, a carbonyl group, an ester group, an amide group, a urethane group, and the like, which may also include a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group , a carbonyl group, a formyl group, an ester group, an amide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a silyl group, or a silyloxy group.

Among these, from the viewpoint of transparency and heat resistance, an alkylene group, a cycloalkylene group, a phenylene group, and a biphenylene group are preferable.

When R ⁷ , R ⁶ , R ⁹ is a monovalent organic group having 1 to 20 carbon atoms, the organic group is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an acyl group (-CO-R). , an ester group (-CO-OR or -O-CO-R), an amide group (-CO-NR ₂ or -NR-CO-R), and other monovalent organic groups. , An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a carbonyl group, a formyl group, an ester group, an amide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, a silyl group, a silyloxy group, etc. may be Here, R is a hydrocarbon group.

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

When the component (B) is one or more (meth)acrylates having one or more (meth)acryloyl groups in the molecule, the (meth)acrylate is not particularly limited, and for example, 2-hydroxyethyl (meth)acrylate ) Acrylates, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, aliphatic (meth) acrylates such as 2-hydroxybutyl (meth) acrylate, 2-Hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl (meth)acrylate, 2-hydroxy-3-(1-naphthoxy) and aromatic (meth)acrylates such as propyl (meth)acrylate and 2-hydroxy-3-(2-naphthoxy)propyl (meth)acrylate.

Among these, from the viewpoint of transparency and heat resistance, aliphatic (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate; Or it is preferable that they are aromatic (meth)acrylates, such as 2-hydroxy-3-phenoxypropyl (meth)acrylate and 2-hydroxy-3-(o-phenylphenoxy)propyl (meth)acrylate.

These compounds can be used individually or in combination of 2 or more types.

When component (B) is a vinyl compound having a structural unit represented by the general formula (17) or a vinyl compound having a carboxy group, there is no particular limitation as these vinyl compounds, and examples thereof include (meth)acrylic acid, crotonic acid, Namic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, mono(2-(meth)acryloyloxyethyl)succinate, mono(2-(meth)acryloyloxyethyl)phthalate, mono (2- (meth) acryloyloxyethyl) isophthalate, mono (2- (meth) acryloyloxyethyl) terephthalate, mono (2- (meth) acryloyloxyethyl) tetrahydrophthalate, mono ( 2-(meth)acryloyloxyethyl)hexahydrophthalate, mono(2-(meth)acryloyloxyethyl)hexahydroisophthalate, mono(2-(meth)acryloyloxyethyl)hexahydroterephthalate , ω-carboxy-polycaprolactone mono(meth)acrylate, 3-vinylbenzoic acid, 4-vinylbenzoic acid, and the like.

Among these, (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, mono(2-(meth)acryloyloxyethyl)succinate, mono(2- (meth)acryloyloxyethyl)tetrahydrophthalate, mono(2-(meth)acryloyloxyethyl)hexahydrophthalate, mono(2-(meth)acryloyloxyethyl)hexahydroisophthalate, mono( It is preferably 2-(meth)acryloyloxyethyl)hexahydroterephthalate.

In addition, vinyl compounds having two or more carboxy groups such as maleic anhydride and citraconic acid anhydride or partially esterified vinyl compounds of some carboxy groups of the acid anhydrides with appropriate alcohols such as methanol, ethanol and propanol are also preferably used. do.

In addition, after copolymerization of an acid anhydride of a vinyl compound having two or more carboxyl groups and a (meth)acrylate compound having one or more (meth)acryloyl groups in a molecule, partial esterification is performed with an appropriate alcohol such as methanol, ethanol, or propanol. A modified vinyl compound is also preferably used.

These compounds can be used individually or in combination of 2 or more types.

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

There is no restriction|limiting in particular as said curable (meth)acrylate (B1), For example, the following urethane (meth)acrylates etc. are mentioned (1)-(4).

(1) Urethane (meth)acrylate obtained by reacting (meth)acrylate which has a bifunctional alcohol compound, a bifunctional isocyanate compound, and a hydroxyl group.

(2) Urethane (meth)acrylate obtained by reacting (meth)acrylate which has a bifunctional alcohol compound, a bifunctional isocyanate compound, and an isocyanate group.

(3) Urethane (meth)acrylate obtained by reacting the (meth)acrylate which has a polyfunctional isocyanate compound and a hydroxyl group.

(4) Urethane (meth)acrylate obtained by reacting the (meth)acrylate which has a polyfunctional alcohol compound and an isocyanate group.

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

The difunctional alcohol compound, that is, the diol compound is not particularly limited, and examples thereof include polyetherdiol compounds, polyesterdiol compounds, polycarbonatediol compounds, polycaprolactonediol compounds, and other diol compounds.

The polyetherdiol compound is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, isobutene oxide, butyl glycidyl ether, butene-1-oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, By ring-opening (co)polymerizing at least one selected from cyclic ether compounds such as 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, cyclohexene oxide, styrene oxide, phenyl glycidyl ether, and benzoic acid glycidyl ester Polyetherdiol compound obtained; polyetherdiol compounds obtained by ring-opening addition of at least one selected from the above cyclic ether compounds to alicyclic diol compounds such as cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F; and hydroquinone; A polyetherdiol compound obtained by ring-opening addition of at least one selected from the above cyclic ether compounds to bifunctional phenolic compounds such as resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AF, biphenol, and fluorene bisphenol; can be heard

The polyester diol compound is not particularly limited, and examples thereof include malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, and fumaric acid. , a bifunctional carboxylic acid compound such as itaconic acid, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, dibutanediol, polybutanediol, pentanediol, neopentylglycol, 3 - polyester polyol compounds obtained by copolymerizing diol compounds such as methyl-1,5-pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanedimethanol, and tricyclodecanediol; can

The polycarbonate diol compound is not particularly limited, and examples thereof include phosgene, triphosgene, dialkyl carbonate, diaryl carbonate, etc., as well as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and butanediol. , dibutanediol, polybutanediol, pentanediol, neopentylglycol, 3-methyl-1,5-pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanedimethanol, tricyclodecanediol and polycarbonate diol compounds obtained by copolymerizing diol compounds such as hydrogenated bisphenol A and hydrogenated bisphenol F.

The polycaprolactonediol compound is not particularly limited, and examples thereof include ε-caprolactone, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, dibutanediol, polybutanediol, Diol compounds such as pentanediol, neopentylglycol, 3-methyl-1,5-pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanedimethanol, and tricyclodecanediol are copolymerized. The obtained polycaprolactone diol compound etc. are mentioned.

Examples of other diol compounds include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, dibutanediol, pentanediol, neopentylglycol, 3-methyl-1,5-pentanediol, hexanediol, and heptanediol. , aliphatic diol compounds such as octanediol, nonanediol, and decanediol; alicyclic diol compounds such as cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F; and modified diol compounds such as polybutadiene-modified diol compounds, hydrogenated polybutadiene-modified diol compounds, and diricone-modified diol compounds.

These diol compounds can be used individually or in combination of 2 or more types.

The bifunctional isocyanate compound is not particularly limited, and examples thereof include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, and dodecamethylene diisocyanate. aliphatic bifunctional isocyanate compounds; 1,3-bis(isocyanatomethyl)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, bicycloheptane tri alicyclic bifunctional isocyanate compounds such as isocyanate; 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-chlorine Aromatic bifunctional isocyanate compounds, such as silylene diisocyanate and m-xylylene diisocyanate, etc. are mentioned.

These compounds can be used individually or in combination of 2 or more types.

The (meth)acrylate having a hydroxyl group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-chloro-2-hydroxypropyl ( meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl (meth) Monofunctional (meth)acrylic such as acrylate, 2-hydroxy-3-(1-naphthoxy)propyl(meth)acrylate, 2-hydroxy-3-(2-naphthoxy)propyl(meth)acrylate, etc. rates, ethoxylated products thereof, propoxylated products thereof, ethoxylated propoxylated products thereof, and caprolactone modified products thereof; Bifunctional (meth)acrylates such as bis(2-(meth)acryloyloxyethyl)(2-hydroxyethyl)isocyanurate, ethoxylated products thereof, propoxylated products thereof, and ethoxylated products thereof propoxylated products, and caprolactone denatured products thereof; Cyclohexanedimethanol type epoxydi(meth)acrylate, tricyclodecanedimethanol type epoxydi(meth)acrylate, hydrogenated bisphenol A type epoxydi(meth)acrylate, hydrogenated bisphenol F type epoxydi(meth)acrylate Acrylate, hydroquinone type epoxydi(meth)acrylate, resorcinol type epoxydi(meth)acrylate, catechol type epoxydi(meth)acrylate, bisphenol A type epoxydi(meth)acrylate, bisphenol F type epoxydi (meth)acrylate, bisphenol AF type epoxydi(meth)acrylate, biphenol type epoxydi(meth)acrylate, fluorene bisphenol type epoxydi(meth)acrylate, isocyanuric acid monoallyl type epoxydi( bifunctional epoxy (meth)acrylates such as meth)acrylate; Trifunctional or higher functional (meth)acrylates such as pentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate, ethoxylated products thereof, and propoxylated products thereof , ethoxylated propoxylated products thereof, and caprolactone modified products thereof; and trifunctional or higher functional epoxy (meth)acrylates such as phenol novolak-type epoxy (meth)acrylate, cresol novolak-type epoxy poly(meth)acrylate, and isocyanuric acid-type epoxytri(meth)acrylate. .

These compounds can be used individually or in combination of 2 or more types.

Here, the ethoxylated product, propoxylated product, and ethoxylated propoxylated product of (meth)acrylate are alcohol compounds or phenolic compounds (eg, monofunctional (meth)acrylate; CH ₂ =CH(R ⁷ )-COO-R ⁸ (represented by HO-R ⁸ when R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a monovalent organic group), the alcohol compound or phenol compound, respectively, one or more ethylene A (meth)acrylate obtained by using an alcohol compound having a structure in which oxide is added, an alcohol compound having a structure in which one or more propylene oxide is added, or an alcohol compound having a structure in which one or more ethylene oxide and propylene oxide are added as raw materials (For example, in the case of ethoxylation, CH ₂ =CH(R ⁷ )-COO-(CH ₂ CH ₂ O) _q -R ⁸ (q is an integer of 1 or more, R ⁷ and R ⁸ are the same as above) represented by ). In addition, the caprolactone modified product refers to (meth)acrylate obtained by using as a raw material an alcohol compound obtained by modifying an alcohol compound as a raw material of (meth)acrylate into ε-caprolactone (for example, monofunctional (meth)acrylate). In the case of a caprolactone modified form of acrylate, it is represented by CH ₂ =CH(R ⁷ )-COO-((CH ₂ ) ₅ COO) _q -R ⁸ (q, R ⁷ , R ⁸ are the same as above)).

The (meth)acrylate having an isocyanate group is not particularly limited, and examples thereof include N-(meth)acryloyl isocyanate, (meth)acryloyloxymethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 2-(meth)acryloyloxyethoxyethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, etc. are mentioned.

These compounds can be used individually or in combination of 2 or more types.

There is no restriction|limiting in particular as said polyfunctional isocyanate compound, For example, the said bifunctional isocyanate compound; Multimers, such as the urethodione dimer of the said bifunctional isocyanate compound, an isocyanurate type, and a biuret type trimer, etc. are mentioned. In addition, the two or three bifunctional isocyanate compounds constituting the multimer may be the same or different.

These compounds can be used individually or in combination of 2 or more types.

The polyfunctional alcohol compound is not particularly limited, and examples thereof include the above bifunctional alcohol compound; trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trifunctional or higher functional alcohol compounds such as tris(2-hydroxyethyl)isocyanurate, and at least one selected from the above cyclic ether compounds adducts obtained by ring-opening addition of , caprolactone-modified products thereof; alcohol compounds obtained by ring-opening addition of at least one selected from the above cyclic ether compounds to trifunctional or higher than trifunctional phenol compounds such as phenol novolac and cresol novolak; and caprolactone modified products thereof.

These compounds can be used individually or in combination of 2 or more types.

The curable type (meth)acrylate having a urethane bond may further contain a carboxyl group as needed from the viewpoint of heat resistance and solubility in an alkaline developer.

The (meth)acrylate having a carboxyl group and a urethane bond is not particularly limited. For example, when synthesizing the above-mentioned urethane (meth)acrylate, a carboxyl group-containing diol compound is used in combination with the diol compound, or the diol compound Urethane (meth)acrylate etc. obtained by using instead are mentioned.

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

These compounds can be used individually or in combination of 2 or more types.

The acid value of the curable (meth)acrylate having a carboxyl group and a urethane bond can be defined so that it can be developed with an alkali developer described later. The acid value is preferably 5 to 200 mgKOH/g, more preferably 10 to 170 mgKOH/g, and particularly preferably 15 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 block isocyanate compound as component (F). (F) component reacts with a component having a hydroxyl group and/or a carboxyl group to generate a crosslinked structure. In this case, the component (B) is preferably a vinyl compound having a hydroxyl group or a carboxyl group, and when it does not have a hydroxyl group or a carboxyl group, it is preferable to blend a compound (E) having a hydroxyl group or carboxyl group.

(F) The polyfunctional blocked isocyanate compound as component is a compound produced|generated by reaction of a polyfunctional isocyanate compound and a blocking agent. In addition, it is a compound temporarily inactivated by a group derived from a blocking agent, and when heated to a predetermined temperature, the group derived from a blocking agent dissociates to form an isocyanate group. When a polyfunctional block isocyanate compound is used, heat resistance and environmental reliability can be improved by forming a new crosslinked structure by reacting an isocyanate group generated from the polyfunctional block isocyanate compound by heating with a hydroxyl group and/or carboxyl group of component (A). .

The polyfunctional isocyanate compound capable of reacting with the blocking agent is not particularly limited, but examples include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, aromatic polyfunctional isocyanate compounds such as 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, and m-xylylene diisocyanate; 1,3-bis(isocyanatomethyl)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, bicycloheptane tri alicyclic polyfunctional isocyanate compounds such as isocyanate; and aliphatic polyfunctional isocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, and dodecamethylene diisocyanate.

The polyfunctional isocyanate compound is preferably a compound containing at least one selected from an alicyclic structure and an aliphatic structure in its molecule from the viewpoint of transparency and heat resistance, and among these, the alicyclic polyfunctional isocyanate compound; The above aliphatic polyfunctional isocyanate compounds are preferred.

In addition, the polyfunctional isocyanate compound may be a multimer such as a urethodione-type dimer, an isocyanurate-type trimer, or a biuret-type trimer, and the two or three polyfunctional isocyanate compounds constituting them are the same. It may or may not be different. In other cases, for example, a combination of different types of polyfunctional isocyanate compounds may be used, such as a combination of an alicyclic polyfunctional isocyanate compound and an aliphatic polyfunctional isocyanate compound.

The above polyfunctional isocyanate compound can be used individually or in combination of 2 or more types.

As the blocking agent, those having active hydrogen are preferable, and examples thereof include malonic acid diester, acetoacetic acid ester, malonic acid dinitrile, acetylacetone, methylene disulfone, dibenzoylmethane, dipivalylmethane, acetone dicarboxylic acid di active methylene compounds such as esters; oxime compounds such as acetone oxime, methyl ethyl ketone oxime, diethyl ketone oxime, methyl isobutyl ketone oxime, and cyclohexanone oxime; Phenol compounds, such as a phenol, an alkyl phenol, and an alkyl naphthol; and lactam compounds such as γ-butyrolactam, δ-valerolactam, and ε-caprolactam.

Among these, from a viewpoint of transparency and heat resistance, the said active methylene compound; the oxime compound; The above lactam compounds are preferred.

The above blocking agent can be used individually or in combination of 2 or more types.

In the curable resin composition of the present invention, the radical polymerization initiator used as component (C) initiates radical polymerization of component (A) and component (B) by heating or irradiation with actinic rays such as ultraviolet rays and visible rays. .

The radical polymerization initiator is not particularly limited as long as it initiates radical polymerization by heating or irradiation with actinic rays such as ultraviolet rays and visible rays, and examples thereof include thermal radical polymerization initiators and photo-radical polymerization initiators.

The thermal radical polymerization initiator is not particularly limited, and examples thereof include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1,1-bis(t-butylperoxy)-3,3 peroxyketals such as 5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, and 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; dialkyl peroxides such as α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide; diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide, and benzoyl peroxide; Peroxycarbonates such as bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, and di-3-methoxybutylperoxydicarbonate ; t-butylperoxypivalate, t-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2 -Ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyiso Propyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurylate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexyl peroxyesters such as monocarbonate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, and t-butylperoxyacetate; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile) ) and the like.

Among these, diacyl peroxides, peroxyesters, and azo compounds are preferable from the viewpoints of curability, transparency, and heat resistance.

The photo-radical polymerization initiator is not particularly limited as long as it initiates radical polymerization by irradiation with actinic rays such as ultraviolet rays and visible rays, and examples thereof include 2,2-dimethoxy-1,2-diphenylethan-1-one and the like. Benzoinketal of; 1-Hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2- α such as methyl-1-propan-1-one, 2-hydroxy-1-{4[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one -Hydroxyketone; Glyoxy, such as methyl phenylglyoxylate, ethyl phenylglyoxylate, 2-(2-hydroxyethoxy)ethyl oxyphenylacetate, 2-(2-oxo-2-phenylacetoxyethoxy)ethyl oxyphenylacetate ester; 2-Benzyl-2-dimethylamino-1-(4-morpholin-4-ylphenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine α- such as -4-ylphenyl)-butan-1-one, 1,2-methyl-1-[4-(methylthio)phenyl]-(4-morpholine)-2-ylpropan-1-one amino ketone; 1,2-octanedione, 1-[4-(phenylthio),2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl], 1-(O-acetyl oxime) and other oxime esters; Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphos phosphine oxides such as pine oxide; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o- Fluorophenyl) -4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4 2,4,5-triarylimidazole dimers such as ,5-diphenylimidazole dimer; Benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzo benzophenone compounds such as phenone; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di Phenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone quinone compounds such as quinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; Benzoin compounds, such as benzoin, methyl benzoin, and ethyl benzoin; benzyl compounds such as benzyldimethylketal; Acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinylheptane): N-phenylglycine, coumarin and the like.

Here, the 2,4,5-triarylimidazole dimer may give a symmetrical compound with the same substituents of the aryl groups at the two triarylimidazole sites, or may give a different and asymmetrical compound. .

Among the above radical photopolymerization initiators, from the viewpoint of curability and transparency, the above α-hydroxy ketones, glyoxy esters, oxime esters, or phosphine oxides are preferable.

The above radical polymerization initiators (thermal radical polymerization initiator, optical radical polymerization initiator, etc.) can be used alone or in combination of two or more types, and can also be used in combination with an appropriate sensitizer.

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

A solvent and other additives can be blended with the curable resin composition of the present invention as needed. In the calculation of the compounding amount in the curable resin composition, volatile components such as solvents to be removed after curing are excluded from the calculation.

In the case of blending the additives, the blending amount of the component (A), component (B), and component (C) is 5 for component (A) with respect to the total of component (A), component (B), and component (C). to 94.9 wt%, component (B) is 5.0 to 85 wt%, and component (C) is 0.1 to 10 wt%. Preferably, component (A) is 30 to 94.9 wt%, component (B) is 5.0 to 60 wt%, and component (C) is 0.1 to 10 wt%, more preferably component (A) is 40 to 80 wt%, (B) component is 10 to 50 wt%, and (C) component is 1 to 5 wt%.

Further, in the curable resin composition for forming an optical waveguide of the present invention, the compounding amounts of component (A), component (B), and component (C) are 10 to 70 wt% for component (A) and 15% for component (B). It is preferable that it is -70 wt%, and 0.1-10 wt% of component (C). In addition, it is preferable to blend a polyfunctional block isocyanate compound as component (F) and a compound having a hydroxyl group or carboxyl group as component (E), and the blending amount of these is 10 to 40 wt% for component (F) and component (E) It is 0-40 wt%. Here, the component (B) is preferably the component (B1), and preferably contains 10 to 70 wt% of vinyl (B2) having a hydroxyl group or a carboxyl group in an amount of 10 to 70 wt%. (E) When component is a vinyl compound which has a hydroxyl group or a carboxyl group, it calculates as a component corresponding to both (B) component and (E) component.

From another viewpoint, it is preferable that the compounding quantity of (F) component is 1-40 mass % with respect to the total amount of (A)-(C) component, when (E) component is not included. Moreover, when containing (E) component, it is preferable that the compounding quantity of (F) component is 1-40 mass % with respect to the total amount of (A)-(C) component and (E) component. When the compounding amount of component (F) is within the above range, the hydroxyl group and/or the carboxyl group of component (E) react with the isocyanate group generated from the polyfunctional block isocyanate compound to form a sufficient cross-linked structure, so that heat resistance is good and toughness is good and brittle. A hardened product without work can be obtained. From the above viewpoint, the blending amount of component (F) is more preferably 3 to 35% by mass, and particularly preferably 5 to 30% by mass.

In the case of a curable resin composition for forming an optical waveguide, when using (meth)acrylate (B1) having a urethane bond as the component (B), (meth)acrylate (B1) having a urethane bond (B) Although it is good also as all components, you may use another vinyl compound as needed.

In the resin composition of the present invention or the resin composition for forming an optical waveguide, if necessary, so-called additives such as antioxidants, anti-yellowing agents, ultraviolet absorbers, visible light absorbers, colorants, plasticizers, stabilizers, and fillers may be added to adversely affect the effects of the present invention. It may be added in a ratio that does not give

Further, these resin compositions may be diluted using an appropriate organic solvent and used as a resin varnish. The organic solvent used herein is not particularly limited as long as it can dissolve the resin composition, and examples thereof include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene and p-cymene; chain ethers such as diethyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, and dibutyl ether; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, and propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butylolactone; carbonic acid esters such as ethylene carbonate and propylene carbonate; Ethylene glycol 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 bifunctional alcohol alkyl ethers such as ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate bifunctional alcohol alkyl ether acetates such as; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and the like.

These organic solvents can be used individually or in combination of 2 or more types. Moreover, it is preferable that the solid content concentration in a resin varnish is 10-80 mass % normally.

When the resin composition or the resin composition for forming an optical waveguide of the present invention is used as a varnish, it is preferably mixed by stirring. The stirring method is not particularly limited, but stirring using a propeller is preferable from the viewpoint of stirring efficiency. The rotational speed of the propeller during stirring is not particularly limited, but is preferably 10 to 1,000 rpm. When the rotational speed of the propeller is 10 rpm or more, each component is sufficiently mixed, and when it is 1,000 rpm or less, the mixing of air bubbles due to rotation of the propeller is reduced. From the above viewpoint, the rotational speed of the propeller is more preferably 50 to 800 rpm, and particularly preferably 100 to 500 rpm.

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

It is preferable to filter this varnish using a filter with a pore diameter of 50 µm or less. By using a filter with a pore diameter of 50 μm or less, large foreign substances and the like are removed, and splashing and the like do not occur during application, and scattering of light is suppressed and transparency is not impaired. From the above viewpoint, it is more preferable to filter using a filter with a pore diameter of 30 μm or less, and it is particularly preferable to filter using a filter with a pore diameter of 10 μm or less.

In addition, when a volatile component is included in the prepared resin varnish or a resin composition that is not a varnish, degassing under reduced pressure is preferable. The defoaming method is not particularly limited, but examples thereof include a method of using a vacuum pump, a beser, and a degassing device equipped with a vacuum device. The pressure at the time of decompression is not particularly limited, but a pressure at which the low-boiling component contained in the resin composition does not boil is preferable. Although there is no particular restriction on the vacuum degassing time, it is preferably 3 to 60 minutes. If the vacuum degassing time 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 does not volatilize and the degassing time can be shortened to improve productivity. there is.

Next, the resin film for forming an optical waveguide according to the present invention will be described.

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

The support film is not particularly limited, and examples thereof include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; Polycarbonate, polyamide, polyimide, polyamideimide, polyetherimide, polyether sulfide, polyether sulfone, polyether ketone, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone, liquid crystal polymer, etc. can be heard

Among these, from the viewpoint of flexibility and toughness, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene ether, polyphenylene sulfide, and polyarray It is preferably polysulfone.

Further, from the viewpoint of improving the peelability from the resin layer, a film subjected to mold 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 may be appropriately changed depending on the target flexibility, but from the viewpoint of film strength and flexibility, it is preferably 3 to 250 μm, more preferably 5 to 200 μm, and particularly 7 to 150 μm. desirable.

A film in which a resin composition for forming an optical waveguide is applied onto a support film may have a three-layer structure comprising a support film, a resin layer, and a protection film by attaching a protective film on the resin layer as necessary.

The protective film is not particularly limited, but from the viewpoints of flexibility and toughness, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polyolefins such as polyethylene and polypropylene are preferred. Further, from the viewpoint of improving the peelability from the resin layer, a film subjected to mold 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 to 250 μm, more preferably 15 to 200 μm, and particularly preferably 20 to 150 μm.

The thickness of the resin layer of the resin film for forming an optical waveguide of the present invention is not particularly limited, but the thickness after drying is preferably 5 to 500 μm in general. Within the above range, the resin film or the cured product of the resin film has sufficient strength and can be sufficiently dried, so that the amount of residual solvent in the resin film does not increase and the cured product of the resin film does not foam when heated.

The resin film for optical waveguide formation obtained in this way can be easily stored by winding it up in a roll shape, for example. Alternatively, a roll-shaped film may be cut into a desired size and stored as a sheet.

Next, an application example in the case where the resin film for forming an optical waveguide of the present invention is used as a resin film for forming a core portion will be described.

The support film in this case is not particularly limited as long as it transmits the actinic light for exposure used for forming the core pattern. there is.

Among these, polyester; It is preferably a polyolefin. Further, from the viewpoint of improving the transmittance of actinic light for exposure and reducing roughness of the sidewall of the core pattern, it is more preferable to use a support film of a highly transparent type. Examples of commercially available support films of such a high transparency type include "Cosmo Shine A1517" and "Cosmo Shine A4100" manufactured by Toyobo Seki Co., Ltd. and "Lumira FB50" manufactured by Toray Industries, Ltd.

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

Next, the case where the resin film for forming an optical waveguide of the present invention is used as a resin film for forming a cladding layer (a resin film for forming an upper cladding layer or a resin film for forming a lower cladding layer) will be described.

The support film in this case is not particularly limited as long as it transmits the actinic light for exposure used for cladding formation, and examples thereof include those described as specific examples of the support film for the above-mentioned resin film for optical waveguide formation. .

Among these, polyester; It is preferably a polyolefin. Further, from the viewpoint of improving the transmittance of actinic light for exposure and reducing roughness of the side wall of the clad pattern, it is more preferable to use a support film of a highly transparent type. As a support film of such a high transparency type, commercially available ones include, for example, Toyobo Seki Co., Ltd. product "Cosmo Shine A1517", "Cosmo Shine A4100", Toray Co., Ltd. product "Lumira FB50" and the like.

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

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

1(a) to (d) show cross-sectional views of the optical waveguide, respectively.

In Fig. 1(a), an optical waveguide 1 is formed on a substrate 5, a core portion 2 made of a resin composition for forming a core portion having a high refractive index, and a resin for forming a cladding layer having a low refractive index. It is composed of a lower cladding layer 4 and an upper cladding layer 3 made of a composition.

(b) to (d) in Fig. 1 show different forms, respectively. (b) shows the form in which the base material 5 is arrange|positioned as a protective film on the outside of the upper cladding layer 3. (c) shows the form in which the base material 5 is arrange|positioned as a protective film on the outer side of both the lower cladding layer 4 and the upper cladding layer 3. Like (d), the form in which the base material as the protective film 5 is not arrange|positioned is shown.

The resin composition for forming an optical waveguide and the resin film for forming an optical waveguide according to the present invention are used for at least one of the lower cladding layer 4, the core portion 2, and the upper cladding layer 3 of the optical waveguide 1. It is good to use them, and it is preferable to use those whose refractive index has been 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 between thin lines or narrow lines) at the time of forming the optical waveguide core pattern can be further improved, and the flatness is excellent. , it becomes possible to form a fine pattern with a small line width or between lines.

In the optical waveguide 1, the material of the substrate 5 is not particularly limited, and examples include a glass epoxy resin substrate, a ceramic substrate, a glass substrate, a silicon substrate, a plastic substrate, a metal substrate, a substrate with a resin layer, and a substrate with a metal layer. A board|substrate, a plastic film, a plastic film with a resin layer, a plastic film with a metal layer, etc. are mentioned.

The optical waveguide 1 may be a flexible optical waveguide by using a flexible and tough substrate as the substrate 5, for example, a support film of the resin film for forming the optical waveguide. It may function as a protective film for the optical waveguide 1. By disposing the protective film, it becomes possible to impart the flexibility and toughness of the protective film to the optical waveguide 1. Also, since the optical waveguide 1 is not stained or damaged, ease of handling is improved.

From the above point of view, there are cases where a form such as (b) to (c) is suitable instead of the form of Fig. 1 (a). In addition, if the optical waveguide has sufficient flexibility and toughness, the protective film can be omitted as in (d).

The thickness of the lower cladding layer 4 is not particularly limited, but is preferably 2 to 200 μm. When it is 2 μm or more, it becomes easy to confine the propagating light inside the core, and when it is 200 μm or less, the thickness of the entire optical waveguide 1 is not too large. In addition, 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 .

There is no particular restriction on the thickness of the resin film for forming the lower cladding layer, and the thickness is adjusted so that the thickness of the lower cladding layer 4 after curing falls within the above range.

The height of the core portion 2 is not particularly limited, but is preferably 10 to 150 μm. If the height of the core part is 10 μm or more, the positioning tolerance does not decrease in coupling with the light-receiving device or optical fiber after forming the optical waveguide. In this case, the coupling efficiency does not decrease. From the above viewpoint, the height of the core portion is more preferably 15 to 130 μm, and particularly preferably 20 to 120 μm. Moreover, there is no restriction|limiting in particular about the thickness of the resin film for core part formation, The thickness is adjusted so that the height of the core part after hardening may fall into the said range.

The thickness of the upper clad layer 3 is not particularly limited as long as the core portion 2 can be embedded, but it is preferably 12 to 500 μm in thickness after drying. The thickness of the upper cladding layer 3 may be the same as or different from the thickness of the lower cladding layer 4 formed initially, but from the viewpoint of embedding the core portion 2, it is preferable to make it thicker than the thickness of the lower cladding layer 4. . In addition, 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 having 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.

Further, the light propagation loss in a light source having a wavelength of 850 nm after carrying out a high-temperature, high-humidity test at a temperature of 85°C and a humidity of 85% for 1000 hours is preferably 0.3 dB/cm or less, more preferably 0.2 dB/cm or less, and 0.1 dB/cm or less is particularly preferred.

In addition, the said high-temperature, high-humidity leaving test means a high-temperature, high-humidity leaving test performed under the conditions according to the JPCA standard (JPCA-PE02-05-01S).

Further, the light propagation loss in a light source having a wavelength of 850 nm after 1000 cycles of 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 0.1 dB/cm or less is particularly preferred.

In addition, the said temperature cycle test means the temperature cycle test performed under the conditions according to JPCA standard (JPCAPE02-05-01S).

Further, the optical propagation loss in a light source having a wavelength of 850 nm after three reflow tests at a maximum temperature of 265°C is preferably 0.3 dB/cm or less, more preferably 0.2 dB/cm or less, and 0.1 dB/cm or less. is particularly preferred.

In addition, the said reflow test means the lead-free solder reflow test performed under the conditions according to JEDEC standard (JEDEC JESD22A113E).

The optical waveguide of the present invention is excellent in transparency, environmental reliability, and heat resistance, and may be used as an optical transmission path of an optical module. As the form of the optical module, for example, an optical waveguide with an optical fiber in which optical fibers are connected to both ends of the optical waveguide, an optical waveguide with a connector in which connectors are connected to both ends of the optical waveguide, an optical waveguide and a printed wiring board combined with an optical waveguide, and an optical waveguide. An optical-to-electrical conversion module combining a waveguide and an optical/electrical conversion element that mutually converts an optical signal and an electrical signal, a wavelength combiner combining an optical waveguide and a wavelength division filter, and the like may be mentioned.

In addition, in the optoelectronic composite substrate, the printed wiring board to be combined is not particularly limited, and examples thereof include rigid substrates such as glass epoxy substrates and ceramic substrates; Flexible substrates, such as a polyimide substrate and a polyethylene terephthalate substrate, etc. are mentioned.

Hereinafter, a manufacturing method for forming an optical waveguide using the resin composition for forming an optical waveguide or the resin film for forming an optical 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 in which a resin layer for forming an optical waveguide is formed on a base material using the above resin composition or film to manufacture the optical waveguide.

The method for forming the resin layer for forming the optical waveguide is not particularly limited, and examples include spin coating, dip coating, spraying, bar coating, roll coating, and curtain coating using a resin composition for forming the optical waveguide. , a method of applying by a gravure coating method, a screen coating method, an inkjet coating method, and the like.

When the resin composition for forming an optical waveguide is diluted with the organic solvent to form a resin varnish for forming an optical waveguide, a drying step may be added after forming the resin layer, if necessary. There is no restriction|limiting in particular as a drying method, For example, heat drying, vacuum drying, etc. are mentioned. Moreover, you may use these together as needed.

As another method of forming the resin layer for forming an optical waveguide, a method of forming the resin layer for forming an optical waveguide by a laminating method using the above resin film for forming an optical waveguide may be mentioned.

Among these, a method of manufacturing by a lamination method using a resin film for forming an optical waveguide is preferable from the viewpoint that an optical waveguide having excellent flatness and a fine pattern having a small line width or line spacing can be formed.

Next, a manufacturing method for forming the optical waveguide 1 using the optical waveguide-forming resin film for the lower cladding layer, the core portion, and the upper cladding layer will be described, but the present invention is not limited thereto.

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 lamination by pressing while heating using a roll laminator or a flat laminator. In addition, the flat plate type laminator in the present invention refers to a laminator in which laminated material is sandwiched between a pair of flat plates and compressed by pressurizing the flat plates. For example, a vacuum pressure type laminator can be preferably used. The lamination temperature is not particularly limited, but is preferably 20 to 130°C, and the lamination pressure is not particularly limited, but is preferably 0.1 to 1.0 MPa. When a protective film is present in the resin film for forming the lower cladding layer, it is laminated after removing the protective film.

In the case of laminating using a vacuum pressure laminator, the resin film for forming the lower cladding layer may be temporarily adhered on the substrate 5 in advance using a roll laminator. Here, it is preferable to perform temporary bonding while compressing from the viewpoint of improving adhesion and followability, and when compressing, it may be performed while heating using a laminator having a heat roll. The lamination temperature is preferably 20 to 150°C, more preferably 40 to 130°C. Within this range, the adhesion between the resin film and the base material is improved, and the resin layer does not flow too much during roll lamination, and a required film thickness is obtained. The lamination pressure is not particularly limited, but is preferably 0.2 to 0.9 MPa, and the lamination speed is not particularly limited, but is preferably 0.1 to 3 m/min.

The lower cladding layer 4 is formed by curing the resin layer for forming the lower cladding layer laminated on the substrate 5 with light and/or heat. Further, the support film of the resin film for forming the lower cladding layer may be removed either before curing or after curing.

The irradiation amount of actinic light when curing the resin layer for forming the lower cladding layer with light is not particularly limited, but is preferably 0.1 to 5 J/cm 2 . In addition, when an actinic ray penetrates a base material, in order to harden efficiently, a double-sided exposure machine which can simultaneously irradiate an actinic ray from both sides can be used. Moreover, you may irradiate actinic light, heating. Moreover, as a treatment before and after photocuring, you may perform heat treatment at 50-200 degreeC as needed.

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

When the support film of the resin film for forming the lower cladding layer functions as the protective film 5 of the optical waveguide 1, the resin film for forming the lower cladding layer is cured under the same conditions as above by light and/or heat without laminating. Thus, the lower cladding layer 4 may be formed.

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

As a second process, a resin film for forming a core portion is laminated on the lower cladding layer 4 in the same manner as in the first process. Here, the resin layer for forming the core portion is designed to have a higher refractive index than the resin layer for forming the lower cladding layer, and is preferably made of a photosensitive resin composition capable of forming the core portion 2 (core pattern) by actinic light. .

As a 3rd process, the core part 2 is exposed. The method of exposing the core portion 2 is not particularly limited. For example, a method of irradiating an image with actinic rays passing through a negative photomask called artwork, or a negative photomask using direct laser writing. A method of directly irradiating an actinic ray on an image without passing it through, etc. are mentioned.

The light source for active light is not particularly limited, and examples include light sources that effectively emit ultraviolet rays such as ultra-high pressure mercury lamps, high-pressure mercury lamps, mercury vapor arc lamps, metal halide lamps, xenon lamps, and carbon arc lamps; and a light source that effectively emits visible light, such as a plaid light bulb for photography and a solar lamp.

It is preferable that it is 0.01-10 J/cm<2>, the irradiation amount of the actinic light at the time of exposing the core part 2 is more preferably 0.03-5 J/cm<2>, More preferably, it is 0.05-3 J/cm<2>. In this range, the curing reaction proceeds sufficiently, the core portion is not lost due to development, and on the other hand, the core portion does not become thick due to excessive exposure and a fine pattern can be formed, which is preferable. Exposure of the core part 2 may be performed through the support film of the resin film for core part formation, or may be performed after removing a support film.

In addition, after exposure, you may perform post-exposure heating as needed from a viewpoint of improving the resolution and adhesiveness of the core part 2. The time from ultraviolet irradiation to post-exposure heating is preferably within 10 minutes, but there is no particular limitation on this condition. The post-exposure heating temperature is preferably 40 to 160 DEG C, and the time is preferably 30 seconds to 10 minutes, but these conditions are not particularly limited.

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

The developing method is not particularly limited, and examples thereof include a spray method, a dip method, a paddle method, a spin method, a brushing method, and a scraping method. Moreover, you may use these developing methods together as needed. The developer is not particularly limited, and examples thereof include an organic solvent, a semi-aqueous developer composed of an organic solvent and water, a water-based alkaline developer composed of an aqueous alkali solution, and a semi-aqueous alkali developer composed of an aqueous alkali solution and an organic solvent. The development temperature is adjusted according to the development preference of the resin layer for forming the core part.

The organic solvent is not particularly limited, and preferably includes organic solvents used for diluting the resin composition for forming optical waveguides. These compounds can be used individually or in combination of 2 or more types. Moreover, you may mix a surface active agent, an antifoaming agent, etc. in an organic solvent. There is no particular limitation as long as it is composed of one or more kinds of organic solvents and water as the semi-conducting developer. The concentration of the organic solvent is preferably 5 to 90% by mass. Further, a small amount of a surfactant, an antifoaming agent, or the like may be incorporated into the semi-absorbent developer.

The base of the aqueous alkali 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; Alkali metal bicarbonates, such as lithium hydrogencarbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate; 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; Ammonium salts, such as ammonium carbonate and ammonium hydrogencarbonate; Organic bases such as tetramethylammonium hydroxide, triethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2-morpholine, etc. can be heard These compounds can be used individually or in combination of 2 or more types.

It is preferable that the pH of an aqueous alkaline developer is 9-14. Further, a surfactant, an antifoaming agent, and the like may be incorporated into the aqueous alkali developing solution.

There is no particular limitation as long as the semi-aqueous alkali developer is composed of an aqueous alkali solution and one or more of the above organic solvents. Further, the organic solvent is not particularly limited, and examples thereof include preferred organic solvents used for diluting the resin composition for forming an optical waveguide. The pH of the quasi-base alkali developer is preferably as low as possible within a range capable of sufficiently developing, preferably pH 8 to 13, and more preferably pH 9 to 12. It is preferable that the concentration of the organic solvent is usually 5 to 90% by mass. Further, a small amount of a surfactant, an antifoaming agent, or the like may be incorporated into the semi-aqua-based alkali developing solution.

As a treatment after development, cleaning may be performed using an organic solvent, a semi-permanent cleaning liquid, or water, if necessary. The cleaning method is not particularly limited, and examples thereof include a spray method, a dip method, a paddle method, a spin method, a brushing method, and a scraping method. Moreover, you may use these cleaning methods together as needed. An organic solvent can be used individually or in combination of 2 or more types. The concentration of the organic solvent in the semipermanent cleaning liquid is usually preferably 5 to 90% by mass. In addition, the cleaning temperature is adjusted according to the development preference of the resin layer for forming the core part.

Exposure and/or heating may be performed as necessary from the viewpoint of improving the curability and adhesion of the core portion 2 as a treatment after development or washing. The heating temperature is not particularly limited, but is preferably 40 to 200° C., and the amount of active light irradiation is not particularly limited, but is preferably 0.01 to 10 J/cm 2 .

As a fifth process, a resin film for forming an upper cladding layer is laminated on the lower cladding layer 4 and the core part 2 in the same manner as in the first and second processes. Here, the resin layer for forming the upper cladding layer is designed to have a lower refractive index than the resin layer for forming the core portion. In addition, it is preferable that the thickness of the resin layer for forming the upper clad is greater than the height of the core portion 2.

In the same manner as in the first step, the upper cladding layer 3 is formed by curing the resin layer for forming the upper cladding layer with light and/or heat. The amount of irradiation of actinic rays when curing the resin layer for forming the upper cladding layer with light is not particularly limited, but is preferably 0.1 to 30 J/cm 2 . In addition, when an actinic ray penetrates a base material, in order to harden efficiently, a double-sided exposure machine which can simultaneously irradiate an actinic ray from both sides can be used. Moreover, 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 and/or after actinic light irradiation is not particularly limited, but is preferably 50 to 200°C. The heating temperature for curing the resin layer for forming the upper cladding layer by heat is not particularly limited, but is preferably 50 to 200°C.

Further, when the support film of the resin film for forming the upper cladding layer needs to be removed, it may be removed before curing or after curing.

Through the above steps, the optical waveguide 1 can be manufactured.

Example

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

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

Molecular weight and molecular weight distribution were measured using GPC (HLC-8120GPC, manufactured by Tosoh Corporation), using tetrahydrofuran as the solvent, a flow rate of 1.0 ml/min, a column temperature of 38°C, and a calibration curve using monodisperse polystyrene.

2) Structure of the copolymer

It was determined by ¹³ C-NMR and ¹ H-NMR analysis using a JNM-LA600 nuclear magnetic resonance spectrometer manufactured by Nippon Denshi. Chloroform-d ₁ was used as the solvent, and a resonance line of tetramethylsilane was used as an internal standard.

3) Interpretation of end groups

Calculation of the terminal group is based on the number average molecular weight obtained from the GPC measurement and the total amount of the monomer obtained from the results of ¹ H-NMR measurement and gas chromatography (GC) analysis, and the solubility having the terminal group from the amount of the derivative used to introduce the terminal group. The number of terminal groups contained in one molecule of the polyfunctional vinyl aromatic copolymer was calculated.

4) Measurement of glass transition temperature (Tg) and softening temperature of cured products

The copolymer solution was uniformly applied to a glass substrate so that the thickness after drying was 20 µm, and heated and dried using a hot plate for 90 to 30 minutes. The resin film obtained together with the glass substrate was set in a TMA (thermo-mechanical analyzer), heated to 220 ° C. at a heating rate of 10 ° C./min under a nitrogen stream, and further subjected to heat treatment at 220 ° C. for 20 minutes to remove the remaining solvent, At the same time, the copolymer was cured. After the glass substrate was allowed to cool to room temperature, the analysis probe was brought into contact with the sample in the TMA measuring device, scanning measurement was performed from 30°C to 360°C at a heating rate of 10°C/min under a nitrogen stream, and the softening temperature was determined by the tangential method. .

Regarding the glass transition temperature, the above test piece was set in a DMA (dynamic viscoelasticity device) measuring device, measured by scanning from 30°C to 320°C at a heating rate of 3°C/min under a nitrogen stream, and measured by the peak top of the tnδ curve Rescued Tg.

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

To evaluate the heat resistance of the copolymer, the sample was set in a TGA (thermal balance) measuring device, measured by scanning from 30°C to 400°C at a heating rate of 10°C/min under a nitrogen atmosphere, and the weight loss at 350°C was measured. It was obtained as heat resistance. On the other hand, in the measurement of heat discoloration resistance, 6.0 g of the copolymer, 4.0 g of benzyl methacrylate, and 0.02 g of t-butylperoxy-2-ethylhexanoate were mixed, heated at 200 ° C. for 1 hour under a nitrogen stream, and Got the cargo. And the heat discoloration resistance was evaluated by visually confirming the amount of discoloration of the obtained hardened|cured material, and classifying it as (circle): no thermal discoloration, (triangle|delta): pale yellow, and x: yellow.

6) Measurement of compatibility

To measure the compatibility of the copolymer with the epoxy resin, 5.0 g of the sample was mixed with 3.0 g of the epoxy resin (liquid bisphenol A-type epoxy resin: manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 828), and a phenol resin (melamine skeleton-based phenol resin: Gun Ai Kaga 2.0 g of PS-6492 manufactured by Kugo Kogyo Co., Ltd. was dissolved in 10 g of methyl ethyl ketone (MEK), and the transparency of the sample after dissolution was visually checked and classified as ○: transparent, △: translucent, ×: opaque or not dissolved Compatibility was evaluated.

Synthesis Example 1

1.28 moles (182.7 mL) of divinylbenzene (a mixture of 1,4-divinylbenzene and 1,3-divinylbenzene, the following examples are the same), ethylvinylbenzene (1-ethyl-4-vinylbenzene, and 1- A mixture of ethyl-3-vinylbenzene, the following examples are the same) 0.97 mol (137.8 mL), 2.00 mol (323.2 mL) of t-butyl methacrylate, and 300 mL of toluene were put into a 2.0 L reactor, and 50 mmol at 50 ° C. A diethyl ether complex of boron trifluoride was added and reacted for 4 hours. After quenching the polymerization solution with an aqueous solution of sodium hydrogencarbonate, the oil layer was washed with pure water three times, devolatilized under reduced pressure at 60°C, and the polymer was recovered. The obtained polymer was weighed, and it was confirmed that 234.6 g of copolymer A was obtained.

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, resonance lines of terminal groups derived from t-butyl methacrylate were observed in copolymer A. The introduced amount (c1) of the structural unit derived from t-butyl methacrylate in the soluble polyfunctional vinyl aromatic polymer calculated from the result of elemental analysis and the number average molecular weight in terms of standard polystyrene was 2.3 (piece/molecule). In addition, it contained 60.1 mol% of structural units derived from divinylbenzene and 39.9 mol% of structural units derived from ethylvinylbenzene in total (excluding terminal structural units). The vinyl group content contained in copolymer A was 36.2 mol% (excluding terminal structural units).

Further, 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 the TGA measurement, the weight loss at 350°C was 2.80 wt% and the heat discoloration resistance was 0. On the other hand, the compatibility with the epoxy resin was ○.

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

Synthesis Example 2

1.28 moles of divinylbenzene (182.7mL), 0.97 moles of ethylvinylbenzene (137.8mL), 2.00 moles of t-butyl acrylate (289.6mL), and 300mL of toluene were put into a 2.0L reactor, and 50 mmol of trifluoride at 50°C. A boron diethyl ether complex was added and reacted for 4 hours. After quenching the polymerization solution with an aqueous solution of sodium hydrogencarbonate, the oil layer was washed with pure water three times, devolatilized under reduced pressure at 60°C, and the polymer was recovered. The obtained polymer was weighed, and it was confirmed that 215.3 g of copolymer B was obtained.

Mn of the obtained copolymer A was 952, Mw was 4490, and Mw/Mn was 4.72. By 13 C-NMR and 1 H-NMR analysis, resonance lines of terminal groups derived from t-butyl acrylate were observed in copolymer B. The introduced amount (c1) of the structural unit derived from t-butyl acrylate in the soluble polyfunctional vinyl aromatic polymer calculated from the result of elemental analysis and the number average molecular weight in terms of standard polystyrene was 2.5 (units/molecule). In addition, it contained 59.3 mol% of structural units derived from divinylbenzene and 40.7 mol% of structural units derived from ethylvinylbenzene in total (excluding terminal structural units). The vinyl group content contained in the copolymer B was 34.7 mol% (excluding terminal structural units).

Further, 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 the TGA measurement, the weight loss at 350°C was 3.04 wt% and the heat discoloration resistance was ○. On the other hand, the compatibility with the epoxy resin was ○.

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

Synthesis Example 3 (Comparative Example)

Divinylbenzene 2.03 mol (288.5 mL), ethylvinylbenzene 0.084 mol (12.0 mL), styrene 2.11 mol (241.7 mL), 2-phenoxyethyl methacrylate 2.25 mol (427.3 mL), butyl acetate 100.0 mL, toluene 1150 mL was introduced into a 3.0 L reactor, and 300 mmol of a diethyl ether complex of boron trifluoride was added at 50 DEG C, followed by reaction for 4 hours. After quenching the polymerization solution with an aqueous solution of sodium hydrogencarbonate, the oil layer was washed with pure water three times, and the reaction liquid mixture was poured into a large amount of methanol at room temperature to precipitate the polymer. The resulting polymer was washed with methanol, filtered, dried and weighed to obtain 282.4 g of copolymer C.

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

Further, 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 the 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 the epoxy resin was Δ.

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

Synthesis Example 4 (Comparative Example)

Divinylbenzene 1.92 mol (273.5 mL), ethylvinylbenzene 0.08 mol (11.4 mL), styrene 2.0 mol (229.2 mL), 2-phenoxyethyl acrylate 2.00 mol (348.1 mL), butyl acetate 250.0 mL, toluene 1000 mL It was charged into a 3.0 L reactor, and 80 mmol of boron trifluoride diethyl ether complex was added at 70°C, followed by reaction for 6 hours. After quenching the polymerization solution with an aqueous solution of sodium hydrogencarbonate, the oil layer was washed with pure water three times, and the reaction liquid mixture was poured into a large amount of methanol at room temperature to precipitate the polymer. The resulting polymer was washed with methanol, filtered, dried and weighed to obtain 164.2 g of Copolymer D.

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

Further, 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 the 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 the epoxy resin was Δ.

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

Synthesis Example 5

1.024 moles of divinylbenzene (146.2mL), 0.776 moles of ethylvinylbenzene (110.2mL), 0.45 moles of styrene (51.7mL), 2.00 moles of t-butyl methacrylate (323.2mL), and 300mL of toluene were put into a 2.0L reactor. Then, 50 mmol of boron trifluoride diethyl ether complex was added at 50°C and reacted for 4 hours. After quenching the polymerization solution with an aqueous solution of sodium hydrogencarbonate, the oil layer was washed with pure water three times, 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.

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

Further, 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 the TGA measurement, the weight loss at 350°C was 3.37 wt% and the heat discoloration resistance was ○. On the other hand, the compatibility with the epoxy resin was ○.

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

Synthesis Example 6

1.024 moles (146.2 mL) of divinylbenzene, 0.776 moles (110.2 mL) of ethylvinylbenzene, 0.45 moles (81.1 g) of divinyl biphenyl, 2.00 moles (323.2 mL) of t-butyl methacrylate, 300 mL of toluene to 2.0 L It was introduced into the reactor, 50 millimoles of a diethyl ether complex of boron trifluoride was added at 50°C, and the mixture was reacted for 4 hours. After quenching the polymerization solution with an aqueous solution of sodium hydrogencarbonate, the oil layer was washed with pure water three times, 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.

Mn of the obtained copolymer F was 913, Mw was 4210, and Mw/Mn was 4.61. By conducting 13 C-NMR and 1 H-NMR analysis, resonance lines of terminal groups derived from t-butyl methacrylate were observed in Copolymer F. The introduced amount (c1) of the structural unit derived from t-butyl methacrylate in the soluble polyfunctional vinyl aromatic polymer calculated from the result of elemental analysis and the number average molecular weight in terms of standard polystyrene was 2.2 (units/molecule). In addition, 47.3 mol% of structural units derived from divinylbenzene, 34.5 mol% of structural units derived from ethylvinylbenzene, and 18.2 mol% of structural units derived from styrene were contained (excluding terminal structural units). The vinyl group content contained in the copolymer F was 32.9 mol% (excluding terminal structural units).

Further, 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 the TGA measurement, the weight loss at 350°C was 2.92 wt% and the heat discoloration resistance was ○. On the other hand, the compatibility with the epoxy resin was ○.

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

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

7) Solution viscosity

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

8) Bending strength and bending elongation at break

For the test piece used in the bending test, the varnish of the curable resin composition was placed on a mold under a vacuum press molding machine, and the solvent was devolatilized under heating and vacuum. Thereafter, the upper mold was raised, hot-pressed in a vacuum state, and held at 200°C for 1 hour to mold 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 a flat plate obtained by molding, and a bending test was performed. The bending strength and bending elongation at break of the prepared bending test piece were measured using a universal testing machine. In addition, for the bending strength and bending elongation at break, those with a value of less than ±10% with respect to the measured value of the standard formulation are ○, those with a value of 10% or more are ◎, and those with a value in the range of -10 to -20% (triangle|delta), the thing used as a value of -20% or less was evaluated as x.

9) Linear expansion coefficient and glass transition temperature

For test pieces used for testing the linear expansion coefficient and glass transition temperature of the curable resin composition, the varnish of the curable resin composition was placed on a flat mold under a vacuum press molding machine, and the solvent was devolatilized under heating vacuum. Thereafter, a spacer of 0.2 mm was inserted, the upper mold was raised, and a flat plate having a thickness of 0.2 mm was molded by performing hot pressing in a vacuum state and holding at 200° C. for 1 hour. 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 a flat plate obtained by molding, set only on the upper chuck of a TMA (thermomechanical analyzer), and heated to 220° C./min at a heating rate of 10° C./min under a nitrogen stream. The temperature was raised to °C and heat treatment was performed at 220 °C for 20 minutes to remove the remaining solvent and remove the molding deformation in the test piece. After the TMA was allowed to cool to room temperature, the lower side of the test piece in the TMA measuring device was also set in an analysis probe, and scan measurement was performed from 30 ° C to 360 ° C at a heating rate of 10 ° C / min under a nitrogen stream, and 0 to 40 ° C. The linear expansion coefficient was calculated from the dimensional change in .

In addition, the glass transition temperature was measured by setting the test piece in a DMA (dynamic viscoelasticity device) measuring device and scanning from 30 ° C. to 320 ° C. at a heating rate of 3 ° C./min under a nitrogen stream, and Tg was obtained by

10) Permittivity and dielectric loss tangent

In accordance with the JIS C2565 standard, a cured product flat test piece after drying and stored for 24 hours in a room at 23 ° C and 50% humidity was used by a cavity resonance technique dielectric constant measuring device manufactured by AT, Inc., and dielectric constant at 18 GHz and the dielectric loss tangent was measured.

In addition, after leaving the cured flat test piece at 85°C and 85% relative humidity for 2 weeks, the dielectric constant and dielectric loss tangent were measured, and the dielectric constant and dielectric loss tangent were measured after the moist heat resistance test.

11) Copper foil peel strength

A glass cloth (E glass, mass per unit area: 71 g/m 2 ) was immersed in the varnish of the thermosetting resin composition, impregnated, and dried in an air oven at 80° C. for 10 minutes. At that time, it was adjusted so that the resin content (R.C) of the obtained prepreg would be 50 wt%.

Using this prepreg, a plurality of layers of the curable composite material are overlapped as necessary so that the thickness after molding is about 0.6 mm to 1.0 mm, and copper foil having a thickness of 18 μm (trade name F2-WS copper foil, Rz: 2.0 μm, Ra: 0.3 μm) was molded and cured by a vacuum press molding machine to obtain a laminate for evaluation. As curing conditions, the temperature was raised at 3°C/min, held at 200°C for 60 minutes at a pressure of 3 MPa, and a copper clad laminate for evaluation was obtained.

A test piece with a width of 20 mm and a length of 100 mm is cut out from the cured laminate obtained in this way, and a parallel incision with a width of 10 mm is made on the surface of the copper foil, and then the copper foil is continuously applied at a rate of 50 mm/min in a direction of 90° to the surface. After peeling, the stress at that time was measured with a tensile tester, and the lowest value of the stress was recorded as copper foil peel strength (based on JIS C 6481).

The test of the copper foil peel strength after the heat-and-moisture resistance test was measured in the same manner as described above after leaving the test piece at 85°C and 85% relative humidity for 2 weeks.

12) Copper plating peel strength

･Production of plated copper laminated board

The copper-clad laminate produced in the preceding paragraph was immersed in an aqueous solution of 150 g/L of ammonium persulfate at 40°C for 20 minutes, and the copper foil was etched away.

Next, the laminated sheet from which the sample was not extracted was immersed in CircuPosite MLB Conditioner 211 (manufactured by Rohm and Haas Japan Co., Ltd., trade name) of an aqueous swelling solution at 80° C. for 5 minutes by a dip method. Further, after washing with running water at room temperature for 3 minutes, immersion treatment was performed at 80°C for 10 minutes by the dip method similarly using CircuPosite MLB Conditioner 211 (trade name, manufactured by Rohm & Haas Japan Co., Ltd.) as an aqueous solution of strong alkali permanganate.

Subsequently, immersion treatment was carried out at 40°C for 5 minutes by the dip method using MLB Nutriizer 216 (product name, manufactured by Rohm & Haas Japan Co., Ltd.) as a neutralization solution. After treatment with flowing water at room temperature for 3 minutes, treatment was performed at 60°C for 5 minutes using conditioner liquid CLC-501 (trade name, manufactured by Hitachi Kasei Kogyo Co., Ltd.), followed by running water washing, and pre-dip liquid PD-201 (trade name, Hitachi Kasei Kogyo Co., Ltd.) in an aqueous solution at room temperature for 3 minutes, treatment in an aqueous solution containing metal palladium liquid HS-202B (trade name, Hitachi Kasei Kogyo Co., Ltd.) for 10 minutes at room temperature, washing with water, and activation Treatment solution ADP-501 (trade name, manufactured by Hitachi Kasei Kogyo Co., Ltd.) was treated at room temperature for 5 minutes in an aqueous solution. Then, using Cust-201 as an electroless copper plating solution, base copper with an electroless copper thickness of 0.5 μm was formed on both sides of the laminate by dipping at room temperature for 15 minutes by a dip method, and further, with electrolytic copper, up to a copper thickness of 20 μm. plating was done.

Then, from the cured laminate for the plating adhesion test, a line having a copper width of 10 mm and a length of 100 mm was processed by etching, and this end was peeled off, held with a gripper, and peeled at room temperature for about 50 mm in the vertical direction in accordance with JIS-C-6421. The lowest value of the load was recorded as the copper plating peel strength.

13) Formability

A core material patterned in a lattice shape with a line width (L) of 0.5 mm and a line spacing (S) of 1.0 mm (L/S = 0.5/1.0 mm) was prepared using the copper-clad laminate for evaluation formed in the preceding paragraph. This core material was subjected to a blackening treatment, and then prepreg was laminated thereon and subjected to secondary molding to prepare a laminated board for evaluation with an inner layer having a lattice pattern. With respect to the prepared laminated substrate for evaluation, it was confirmed whether or not defects such as voids due to lack of flowability of the resin varnish, for example, occurred. Thereafter, this laminated board for evaluation was immersed in boiling water for 4 hours, and then immersed in a solder bath at 280°C. At that time, the existence of voids could not be confirmed, and even after being immersed in the soldering tank, the occurrence of defective phenomena such as expansion, delamination, and misling (white spots) was evaluated as "○", and voids, swelling, and delamination , Mizuring (white spots) was evaluated as "x" when the occurrence of either was confirmed.

<Description of symbols in the table>

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

Modified PPE-B: polyphenylene oligomer having vinyl groups at both ends (Mn = 2270, manufactured by Mitsubishi Gas Chemical Co., Ltd., 2,2',3,3',5,5'-hexamethylbiphenyl-4 Reaction product of 4'-diol 2,6-dimethylphenol polycondensate and chloromethylstyrene)

Modified PPE-C: polyphenylene oligomer having a vinyl group at one end (Mn = 2340, reaction product of polyphenylene ether (SA120 manufactured by SABIC Innovative Plastics) and chloromethyl styrene)

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 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) o-cresol novolac type epoxy resin: Epototo YDCN-700-3 (low-viscosity type, manufactured by Nippon-Stetsu Sumikin Kaga) Ku Kabushiki Kaisha product)

Bisphenol F-type liquid epoxy resin: Epicoat 806L, Mw = 370 (manufactured by Japan Epoxy Resin Co., Ltd.)

Naphthalene backbone liquid epoxy resin: EPICLON HP-4032D, Mw=304 (manufactured by DIC Corporation)

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

Bisphenol A type liquid epoxy resin: Epicoat 828US, Mw = 370 (manufactured by Japan Epoxy Resin Co., Ltd.)

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

Biphenyl backbone phenolic resin: Meiwa Kasei Co., Ltd., MEH-7851-S

Melamine skeleton system phenolic resin: Gunei Chemical Co., Ltd., PS-6492

Allyl group-containing skeleton phenolic resin: YLH-903, manufactured by Japan Epoxy Resin Co., Ltd.

Alicyclic skeletal acid anhydride: Nippon Chemical Co., Ltd., MH-700

Aromatic skeleton acid anhydride: Sartomer Japan Co., Ltd., SMA Resin EF60

Styrene-based copolymer: KRATON A1535 (manufactured by Kraton Polymers LLC)

Phenoxy resin: weight average molecular weight 37000, Mitsubishi Chemical Corporation "YL7553BH30" (1: 1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass)

Amorphous spherical silica: made by Adomatex, SE2050 SPE, average particle diameter 0.5 μm (processed 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 a curing accelerator and antioxidant were dissolved in 8.6 g of toluene to obtain a curable resin composition (varnish A).

The prepared varnish A was dropped onto a lower mold, and after evaporation of the solvent under reduced pressure at 130 ° C., the mold was piled up, and a vacuum press was performed under conditions of 200 ° C. and 3 MPa for 1 hour to heat cure. Various characteristics including the dielectric constant and dielectric loss tangent at 18 GHz were measured for the cured flat plate test piece of the obtained thickness: 0.2 mm. In addition, after leaving the cured flat test piece at 85°C and 85% relative humidity for 2 weeks, the dielectric constant and dielectric loss tangent were measured, and the dielectric constant and dielectric loss tangent were measured after the moist heat resistance test. The results obtained by these measurements are shown in Table 1.

Examples 6 to 8, Comparative Examples 3 to 4

A curable resin composition (varnish) was obtained in the same manner as in Example 5 except that it was made according to the formulation shown in Table 1. Then, in the same manner as in Example 5, a cured product flat test piece was created, 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 in a similar manner to Example 5, except that it was formulated according to the formulations shown in Tables 2 and 3. Then, in the same manner as in Example 5, a cured product flat test piece was created, and the same items as in Example 5 were tested and evaluated. The results obtained by these tests are shown in Table 1. In addition, using the varnishes shown in these Examples and Comparative Examples, prepregs, copper-clad laminates for tests, and laminates with plating for tests were prepared according to the methods described in test methods 11) to 13), copper foil peel strength, Copper plating peeling strength and moldability were evaluated. The test results are shown in Table 2 and Table 3.

Examples 21 to 30 and Comparative Examples 11 to 12

Copolymers A to F obtained in Synthesis Examples 1 to 6 were used to form curable resin compositions.

The copolymers, acrylates, polymerization initiators, and additives shown in Tables 4 and 5 were mixed in the ratio (weight ratio) shown in Tables 4 and 5 to obtain a curable resin composition. Here, in Examples and Comparative Examples shown in Tables 4 and 5, except for Example 29, the resin composition obtained by mixing with the formulation described in the table was molded into a test piece for evaluation as it was. In Example 29, in order to facilitate the dissolution of the stabilizer and the initiator, 30 parts by weight of toluene was added as a solvent to 100 parts by weight of the resin component to obtain a resin varnish in which each component was dissolved, and the resin varnish immediately before molding was subjected to vacuum devolatilization at 50°C, and the resin composition after removal of the solvent was used as a test piece.

In the formulations in which only the thermal initiator was added to the test piece (Examples 21 to 28 and Comparative Examples 11 to 12), the curable resin composition was placed on the lower mold, and b-staged in a heated vacuum state. After the viscosity of the resin composition rises and becomes viscous, the upper mold is placed on the lower mold, the mold is placed on the heating plate of the vacuum press molding machine, hot press is performed in a vacuum state, and cured to a thickness of 1.0 mm by holding at 200 ° C. for 1 hour. Resin plate A1 was molded. On the other hand, in the formulation containing the UV initiator (Examples 29 to 30), a 1.0 mm thick silicone rubber spacer is used between two glass plates of 50 mm in width, 50 mm in length and 1.0 mm in thickness, and a gap of 1.0 mm is formed. , the composition was injected into a glass mold fixed by wrapping the outer periphery with polyimide tape, and irradiated with ultraviolet rays for several seconds from one side of the glass mold with a high-pressure mercury lamp for primary curing. Cured resin flat plate A2 was molded by placing in an inert gas oven and heating at 200°C for 1 hour.

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

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

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

The results of these measurements are shown in Tables 4 and 5.

7) Solution viscosity

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

8) Bending strength and bending elongation at break

A test piece A having a width: 5.0 mm, a thickness: 1.0 mm, and a length of 120 mm was prepared. Bending strength and bending elongation at break were measured using a universal testing machine. In addition, for the bending strength and bending elongation at break, a value of less than ±10% with respect to the measured value of the standard formulation is ○, a value of 10% or more is ◎, and a value in the range of -10 to -20% A thing having a value of Δ and -20% or less was evaluated as x.

9) Linear expansion coefficient and glass transition temperature

A test piece B having a width: 3.0 mm, a thickness: 0.2 mm, and a length: 40 mm was prepared. The mold deformation in the test piece was removed by setting only the upper chuck of a TMA (thermomechanical analyzer), raising the temperature to 220 ° C. at a heating rate of 10 ° C./min under a nitrogen stream, and further heat treatment at 220 ° C. for 20 minutes. . After the TMA was allowed to cool to room temperature, the lower side of the test piece in the TMA measuring device was also set in an analysis probe, and scan measurement was performed from 30 ° C to 360 ° C at a heating rate of 10 ° C / min under a nitrogen stream, and 0 to 40 ° C. The linear expansion coefficient was calculated from the dimensional change in . In addition, the glass transition temperature was determined by the tangential method.

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

10) Measurement of refractive index

The refractive index and Abbe's number were measured with an Abbe refractometer (manufactured by Atago Co., Ltd.) using a test piece A having a thickness of 1.0 mm.

12) Color

Using a test piece A having a thickness of 1.0 mm, measurement was performed with a color difference meter (trade name "MODEL TC-8600", manufactured by Tokyo Denshoku Co., Ltd.), and the YI value was shown.

13) Haze (turbidity) and total light transmittance

Using a test piece B having a thickness of 0.2 mm, haze (turbidity) and total light transmittance were measured using an integral formula light transmittance measuring device (Nippon Denshoku Co., Ltd., SZ-Σ90).

14) Release form, mold reproducibility, and burr, mole

In the formulation in which only the thermal initiator was added (Examples 21 to 28 and Comparative Examples 11 to 12), the curable resin composition was placed on the lower mold, and b-staging was performed under heating vacuum. After the viscosity of the resin composition rises and becomes viscous, the upper mold is placed on the lower mold, the mold is placed on the heating plate of the vacuum press molding machine, hot press is performed in a vacuum state, and the temperature is maintained at 200 ° C. for 1 hour, while containing a UV initiator. In the formulations (Examples 29 to 30), the curable resin composition was placed on a mold having a cavity in the shape of a spherical lens with a diameter of 3.0 mm, a glass upper mold was placed on the lower mold, and a high-pressure mercury lamp was used from the upper surface of the glass upper mold, After primary curing by irradiation with ultraviolet rays for several seconds, the glass mold was placed in an inert gas oven under a nitrogen gas stream and heated at 200° C. for 1 hour to mold a spherical lens having a diameter of 3.0 mm. Molding of the hooked spherical lens was repeated 5 times, and the releasability was evaluated by the difficulty of releasing the cured resin lens from the mold.

○····Good releasability from the mold

△・・・・Slightly difficult to release

×・・・・It is difficult to release the mold or there is a remainder of the mold

Mold reproducibility was evaluated by observing the surface shape of the cured resin lens and the surface shape of the mold.

○・・・・Good reproducibility

×・・・Poor reproducibility

Burrs and moles were evaluated according to the size of burrs generated outside the part of the molded product when the cured resin lens was released from the mold, and the degree of mixing of the resin with the clearance of the mold.

○····The size of the burr is less than 0.05 mm, and the blending of the resin is less than 1.0 mm

△... Burr size less than 0.2mm, resin blend less than 3.0mm

×····The size of the burr is 0.2 mm or more, and the blending of the resin is 3.0 mm or more

15) Reflow heat resistance

Spectral transmittance at a wavelength of 400 nm was measured with a spectrophotometer CM-3700d (manufactured by Konica Minolta Co., Ltd.) using a test piece A having a thickness of 1.0 mm. The measurement timing was before the heat resistance test performed post-curing at 190°C for 60 minutes and after the heat resistance test at 260°C for 8 minutes in an air oven.

<Description of symbols in the table>

Pancryl FA-BZA; Benzyl Acrylate, manufactured by Hitachi Kasei Kogyo Co., Ltd.

Pancryl FA-302A; manufactured by Hitachi Kasei Kogyo Co., Ltd., o-phenylphenoxyethyl acrylate

Light acrylate PO-A: Kyoeisha Chemical Co., Ltd. product, phenoxyethyl acrylate

OGSOL EA-0200: Acrylate containing fluorene skeleton, manufactured by Osaka Gas Chemical Co., Ltd.

Light acrylate TMP-A: Kyoeisha Chemical Co., Ltd. product, trimethylolpropane triacrylate

Adekastab AO-412S: Adekaze Co., Ltd., pentaerythritol-tetrakis (dodecylthiopropionate)

Adecastab AO-60: Adekase Co., Ltd., pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]

Perbutyl O: manufactured by Nippon Oil Industry Co., Ltd., t-butyl-peroxy-2-ethylhexanoate

Irgacure® manufactured by Chiba Specialty Chemicals, 1-hydroxy-cyclohexyl-phenyl-ketone

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, and stirring was performed while introducing nitrogen gas. The temperature was raised to 65 ° C., 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, 2,2'-azobis ( A mixture of 3 parts by weight of 2,4-dimethylvaleronitrile), 49 parts by weight of propylene glycol monomethyl ether acetate, and 20 parts by weight of methyl lactate was added dropwise over 3 hours, followed by stirring at 65°C for 3 hours, and further at 95°C. Stirring was continued for 1 hour to obtain a solution of copolymer G (solid content: 45% by mass). Mn of obtained copolymer G was 16700, Mw was 38100, Mw/Mn was 2.28, and the acid value was 79 mgKOH/g.

Preparation Example 1

(A) 10 parts by weight of copolymer A as component, (E) 62 parts by weight (solid content: 45 mass%) of the copolymer G solution (solid content: 28 mass%), (B) component, a polyester skeleton 33 parts by mass of urethane (meth)acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd. "U-200AX") and urethane (meth)acrylate having a polypropylene glycol skeleton (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) "UA-4200") 15 parts by mass, (F) component, polyfunctional block isocyanate solution in which isocyanurate-type trimers of hexamethylene diisocyanate are protected with methyl ethyl ketone oxime (solid content 75 mass%) (Sumika Bayer "Smidul BL3175" manufactured by Urethane Co., Ltd.) 20 parts by mass (solid content 15 parts by mass), (C) As a photopolymerization initiator of component, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy -2-methyl-1-propan-1-one (“Irgacure 2959” manufactured by Chiba Japan Co., Ltd.) 1 part by mass, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Chiba Japan Co., Ltd.) 1 part by mass of "Irgacure 819") and 23 parts by mass of propylene glycol monomethyl ether acetate as an organic solvent for dilution were mixed while stirring. After pressure filtration using a polypropylene filter having a pore diameter of 2 µm, degassing under reduced pressure was performed to obtain a resin varnish W-I for forming a cladding layer.

Preparation Example 2

The varnish W-I was applied on the untreated surface of a PET film ("Cosmo Shine A4100" manufactured by Toyobo Seki Co., Ltd., thickness 50 µm) using the above coating machine, and after drying at 100 ° C. for 20 minutes, the surface as a cover film. A release-treated PET film ("Purex A31" manufactured by Teijin DuPont Film Co., Ltd., thickness: 25 µm) was attached to obtain a resin film F-I for cladding layer formation. At this time, the thickness of the resin layer was adjusted so that the film thickness after curing was 20 μm for the resin film for forming the lower cladding layer and 60 μm for the resin film for forming the upper cladding layer.

Preparation Example 3

Copolymer A 15 parts by weight, copolymer G solution 33.3 parts by weight (solid content 15 parts by weight), 2-methacryloyloxyethylsuccinic acid ("Light Ester HO-MS" manufactured by Kyoeisha Chemical Co., Ltd.) 10 20 parts by weight of urethane (meth)acrylate having a polyester skeleton ("U-108A" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), EO adduct diacrylate of bisphenol A (Hitachi Chemical Industry Co., Ltd.) 20 parts by weight of "Pancryl FA-321A") and 20 parts by weight of polyfunctional block isocyanate solution (75% by weight of solid content) ("Smidur BL3175" manufactured by Sumika Bayer Urethane Co., Ltd.) (15 parts by weight of solid content) 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by BASF Japan Co., Ltd.; Irgacure 2959) 1 part by weight and 1 part by weight of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by BASF Japan Co., Ltd.; Irgacure 819) and 19 parts by weight of propylene glycol monomethyl ether acetate were added and mixed while stirring. . After pressure filtration using a polypropylene filter with a pore diameter of 2 µm, degassing under reduced pressure was performed to obtain a resin varnish W-II for forming a core portion.

Production Example 4

The resin varnish W-II for forming the core portion was applied onto the untreated surface of a PET film ("Cosmo Shine A1517" manufactured by Toyobo Seki Co., Ltd., thickness 16 µm) using a coater, and at 80°C for 10 minutes at 100 °C. After drying at °C for 10 minutes, a surface release treated PET film (manufactured by Teijin DuPont Film Co., Ltd.; Purex A31, thickness: 25 µm) was attached as a protective film to obtain a resin film for core formation F-II. At this time, the thickness of the resin layer was adjusted so that the film thickness after curing was 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 (thickness: 50 µm) under conditions of a pressure of 0.5 MPa and a temperature of 80°C. Moreover, it crimped|bonded under the conditions of the pressure of 0.4 Mpa, and the temperature of 80 degreeC using the vacuum pressure type laminator.

Next, the supporting film was removed after irradiation with ultraviolet rays (wavelength: 365 nm) at 2000 mJ/cm 2 using an ultraviolet exposure machine. Thereafter, the lower cladding layer 4 was formed by curing by heating at 160°C for 1 hour.

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

Subsequently, ultraviolet rays (wavelength: 365 nm) were irradiated at 1000 mJ/cm 2 with an ultraviolet ray exposure machine through a negative photomask having a width of 50 μm, and the core portion 2 (core pattern) was exposed. After performing post-exposure heating at 80 degreeC, the support film was removed and it developed using propylene glycol monomethyl ether acetate/N,N-dimethylacetamide (70/30 mass ratio). Then, after washing with propylene glycol monomethyl ether acetate, washing was performed with 2-propanol. After drying, it was cured by heating at 160°C for 1 hour.

Next, using a vacuum pressure laminator, the resin film F-I for forming the upper cladding layer from which the protective film was removed was laminated on the core portion 2 and the lower cladding layer 4 under conditions of a pressure of 0.4 MPa and a temperature of 100°C. The upper cladding layer 3 was formed by irradiating with ultraviolet rays (wavelength: 365 nm) at 2000 mJ/cm 2 , removing the support film, and curing by heating at 160° C. for 1 hour. Thereafter, the surface release-treated PET film was removed to obtain an optical waveguide 1 shown in FIG. 1(d). After that, a flexible optical waveguide with a length of 10 cm was cut using a dicing saw.

The following evaluation was performed about the obtained flexible optical waveguide.

[Optical Propagation Loss Measurement]

The light propagation loss of the obtained flexible optical waveguide is measured by a VCSEL ("FLS-300-01-VCL" manufactured by EXFO), a light-receiving sensor ("Q82214" manufactured by Advantist Co., Ltd.), incident light having a light source having a wavelength of 850 nm as a center wavelength, The measurement was performed using a fiber (GI-50/125 multimode fiber, NA = 0.20) and a radiated fiber (SI-114/125, NA = 0.22). The optical propagation loss was calculated by dividing the optical loss measurement value (dB) by the optical waveguide length (10 cm), and evaluated according to the criteria shown in Table 8.

[High temperature and high humidity test]

The resulting flexible optical waveguide was tested using a high-temperature, high-humidity tester ("PL-2KT" manufactured by Espek Co., Ltd.) under conditions in accordance with the JPCA standard (JPCA-PE02-05-01S) at a temperature of 85°C and a humidity of 85%. A standing test was carried out for 1000 hours.

The light propagation loss of the optical waveguide after the high-temperature, high-humidity test was measured using the light source, light-receiving element, incident fiber, and exit fiber as described above, and evaluated according to the criteria shown in Table 8.

[Temperature Cycle Test]

The resulting flexible optical waveguide was tested at a temperature between -55°C and 125°C under conditions conforming to the JPCA standard (JPCA-PE02-05-01S) using a temperature cycle tester ("ETAC WINTECH NT1010" manufactured by Kusumoto Kasei Co., Ltd.) A cycle test was conducted for 1000 cycles. Table 6 shows the detailed temperature cycle test conditions.

The light propagation loss of the optical waveguide after the temperature cycle test was measured using the same light source, light receiving element, incident fiber and exit fiber as described above, and evaluated according to the criteria shown in Table 8.

[Reflow test]

The resulting flexible optical waveguide was subjected to a reflow test at a maximum temperature of 265°C under conditions in accordance with IPC/JEDEC J-STD-020B using a reflow tester ("Saramanda XNA-645PC" manufactured by Furukawa Denki Kogyo Co., Ltd.). It was performed 3 times under a nitrogen atmosphere. Table 7 shows detailed reflow conditions, and the temperature profile in the reflow furnace is shown in FIG. 2 .

The light propagation loss of the optical waveguide after the reflow test was measured using the same light source, light receiving element, incident fiber and exit fiber as described above, and evaluated according to the criteria shown in Table 8.

Table 9 shows the evaluation of the flexible optical waveguide obtained in Example 31.

The cured product obtained from the terminal-modified soluble polyfunctional vinyl aromatic copolymer or material containing the same of the present invention is useful as various electrical insulating materials or materials for laminates in that it has improved heat resistance, compatibility and toughness, and has excellent low dielectric properties. . In addition, the curable resin composition of the present invention is excellent in transparency, heat resistance, and toughness, enables high-precision thick film formation, and is useful not only as a curable resin composition for transparent materials but also particularly for forming optical waveguides.

Reference Numerals 1: optical waveguide, 2: core, 3: upper clad layer, 4: lower clad layer, 5: substrate

Claims (27)

A copolymer having a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit, and terminal groups represented by the following formula (2) and the following formula (3), which is solvent soluble and has polymerizability. Terminal modified soluble polyfunctional vinyl aromatic copolymer characterized by.

(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 a methyl group.) According to claim 1,
A terminal-modified soluble polyfunctional vinyl aromatic copolymer in which the divinyl aromatic compound (a) unit contains a structural unit having no vinyl group and a structural unit having one vinyl group. According to claim 1,
A terminal modified soluble polyfunctional vinyl aromatic copolymer having a number average molecular weight (Mn) of 300 to 100,000 and a molecular weight distribution (Mw/Mn) of 100.0 or less. According to any one of claims 1 to 3,
The introduced amount (c1) of the terminal group represented by the above formula (3) is expressed by the following formula (4)
(c1)≥1.0 (unit/molecule) (4)
is satisfied, and the mole fraction (a) of the structural unit derived from the divinyl aromatic compound and the mole fraction (b) of the structural unit derived from the monovinyl aromatic compound in the copolymer are expressed by the following formula (5)
0.05≤(a)/{(a)+(b)}≤0.95 (5)
is satisfied, and the molar fraction (c) of the terminal groups represented by the above formulas (2) and (3) is expressed by the following formula (6)
0.005≤(c)/{(a)+(b)}<2.0 (6)
, and is also soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. A method for producing the terminal-modified soluble polyfunctional vinyl aromatic copolymer according to claim 1,
A divinyl aromatic compound (a), a monovinyl aromatic compound (b), and a (meth)acrylic acid ester compound (c) represented by the following formula (1) are selected from the group consisting of a Lewis acid catalyst, an inorganic strong acid, and an organic sulfonic acid. A method for producing a terminal-modified soluble polyfunctional vinyl aromatic copolymer, characterized in that polymerization is performed in the presence of at least one catalyst (d).

(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 a methyl group.) According to claim 5,
5 to 95 mol% of divinyl aromatic compound (a) and 95 to 5 mol% of monovinyl aromatic compound (b) relative to 100 mol% of the total of divinyl aromatic compound (a) and monovinyl aromatic compound (b) 0.5 to 500 moles of the (meth)acrylic acid ester compound (c) represented by Formula (1), based on 100 moles of all monomers, and 0.001 to 500 moles of the catalyst (d) based on 1 mole of the (meth)acrylic acid ester compound (c). A method for producing a terminal-modified soluble polyfunctional vinyl aromatic copolymer in which 10 moles of each are used and polymerization raw materials containing them are polymerized in a homogeneous solvent having a dielectric constant of 2.0 to 15.0. A curable composition comprising the terminal-modified soluble polyfunctional vinyl aromatic copolymer according to claim 1 and a radical polymerization initiator. According to claim 7,
A curable composition characterized by further containing modified polyphenylene ether (XC). According to claim 7 or 8,
An epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, an epoxy resin having two or more epoxy groups and a cyanurate structure in one molecule, and/or an epoxy resin having two or more epoxy groups and an alicyclic structure in one molecule. A curable composition characterized by further containing at least one epoxy resin (XD) selected from the group and a curing agent (XE). A cured product formed by curing the curable composition according to claim 7 or 8. A film formed by molding the curable composition according to claim 7 or 8 into a film shape. A curable composite material comprising the curable composition according to claim 7 or 8 and a base material, wherein the base material is contained in a proportion of 5 to 90% by weight. A cured composite material obtained by curing the curable composite material according to claim 12. A laminate characterized by comprising a layer of the cured composite material according to claim 12 and a thin metal layer. Metal foil with resin characterized by having a film formed from the curable composition according to claim 7 or 8 on one side of the metal foil. A varnish for circuit board materials obtained by dissolving the curable composition according to claim 7 or 8 in an organic solvent. Component (A): A copolymer having a divinyl aromatic compound (a) unit and a monovinyl aromatic compound (b) unit, and terminal groups represented by the following formula (2) and the following formula (3), solvent-soluble, A terminal modified soluble polyfunctional vinyl aromatic copolymer having polymerizability,

(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 a methyl group.)
Component (B): at least one vinyl compound having at least one unsaturated group in the molecule, and
(C) component: containing a radical polymerization initiator,
A curable resin composition characterized in that the blending amount of component (A) is 5 to 94.9 wt%, the blending amount of component (B) is 5.0 to 85 wt%, and the blending amount of component (C) is 0.1 to 10 wt%. 18. The method of claim 17,
A curable resin composition characterized in that component (B) contains at least one type of (meth)acrylate having at least one (meth)acryloyl group in a molecule. 18. The method of claim 17,
(B) A curable resin composition characterized by containing a (meth)acrylate having a hydroxyl group and/or a carboxyl group in its molecule. A curable resin composition for forming an optical waveguide, characterized in that the curable resin composition according to claim 17 is for forming an optical waveguide. 18. The method of claim 17,
(C) Curable resin composition characterized by the component containing an optical radical polymerization initiator. 18. The method of claim 17,
(B) A curable resin composition characterized by containing a vinyl compound having a structural unit represented by the following general formula (16) or (17) or a curable vinyl polymer generated from the vinyl compound.

(Wherein, R ⁵ represents a hydrogen atom or a methyl group, X ¹ is a single bond, or an ester bond, an ether bond, a thioester bond, a thioether bond, and an amide bond. Contains at least one bond selected from the group consisting of Represents a divalent organic group having 1 to 20 carbon atoms, which may be present. R ⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.)

(Wherein, 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 a single bond, or an ester bond, an ether bond, a thioester bond, or a thioether bond Represents a divalent organic group having 1 to 20 carbon atoms which may contain at least one bond selected from the group consisting of bonds and amide bonds. R ⁹ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.) A resin film for forming an optical waveguide formed by using the curable resin composition according to any one of claims 17 to 22. An optical waveguide having a core portion and/or a cladding layer formed using the curable resin composition according to any one of claims 17 to 22. An optical waveguide having a core portion and/or a cladding layer formed by using the resin film for forming an optical waveguide according to claim 23. 25. The method of claim 24,
An optical waveguide having an optical propagation loss of 0.3 dB/cm or less in a light source with a wavelength of 850 nm. 26. The method of claim 25,
An optical waveguide having an optical propagation loss of 0.3 dB/cm or less in a light source with a wavelength of 850 nm.

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