TWI600681B - Diethyl ether compounds and resin compositions having a tau skeleton - Google Patents

Description

Diether compound and resin composition having an anthracene skeleton

The present invention relates to a bis-ether compound having an anthracene skeleton, a method for producing a bis(meth) acrylate compound, an aromatic dihalomethyl compound as the intermediate, and a resin composition containing the same.

In recent years, with the progress of miniaturization of electronic equipment, in order to achieve high integration of electronic components, multilayering of printed wiring boards has been carried out, so that a so-called build-up method of alternately forming and laminating insulating layers and conductive layers has been added. . Further, for the resin insulating material used therein, in order to reduce heat loss due to high-speed processing of information and high frequency of signals, a low dielectric constant is required.

A light- or thermosetting resin composition is known as Japanese Patent Publication No. 6-1938, but the dielectric constant is not lowered to a satisfactory level. On the other hand, as a method of achieving a low dielectric constant, as disclosed in Japanese Laid-Open Patent Publication No. 2000-208889 or No. 2001-126534, a method of filling a filler or having a hole is known. Technology, but in the use of encapsulated interlayer insulating film, Has the disadvantage of poor reliability. Further, Japanese Laid-Open Patent Publication No. 2004-300326 discloses a compound containing a photopolymerizable (meth) acrylate (B) having an epoxy group with respect to a specific unsaturated compound (A). (C), and a photopolymerization initiator or a sensitizer (D) light or thermosetting resin composition, which contains 50 mmol or more of methacrylonitrile per 100 g of the resin component as a resin after curing. The light or thermosetting resin composition can have both a low dielectric constant and a high reliability. However, it does not satisfy the low dielectric properties that have recently been required.

On the other hand, an imaging unit used in a mobile phone or the like is generally a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal-Oxide Semiconductor) image sensor. A solid-state imaging element, and a lens unit formed on a photosensitive surface of the solid-state imaging element. In recent years, lenses including lenses made of heat or photocurable resin which are inexpensive and excellent in formability have been used as lenses for lenses. In addition, in optical articles and optical lenses in which a curable resin composition is used as a center of an imaging lens, various optical characteristics are required to be improved. Examples of characteristics required for improvement in optical characteristics include, for example, improvement in characteristics such as low specific gravity, high transparency, low yellowness, high refractive index, high Abbe's Number, and toughness. In particular, in an image pickup unit used for a mobile phone or the like in recent years, it is strongly required to be thinner due to the demand for reduction in thickness of the casing and increase in capacity of the battery. In order to achieve thinning of the lens constituting the lens unit, it is necessary to achieve a high refractive index of the optical lens material.

Japanese Laid-Open Patent Publication No. 2008-94987 discloses a high refractive index resin composition for an optical material having a difunctional (meth) acrylate compound having a bisphenol fluorene skeleton, and a cured product thereof. And a monofunctional (meth) acrylate compound having a biphenyl skeleton. However, the optical lens thus obtained cannot satisfy the high refractive index required for the thinning of the lens unit in recent years, and the dimensional stability is also insufficient.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 6-1938

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-208889

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-126534

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-300326

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-94987

The present invention provides a bis(methyl) acrylonitrile-terminated benzyl ether capable of imparting a cured product having a high dielectric property (low dielectric constant, low dielectric tangent) and high glass transition temperature and flame retardancy. Compound. Further, the present invention provides an aromatic dihalomethyl compound having an intermediate for a benzyl ether compound as a bis(meth)acryl oxime group. Further, the present invention provides a bis(meth)acryl oxime group A curable composition of a benzyl ether compound at the end, and obtained from the curable composition, and can be used as an excellent dielectric material, insulating material, and heat resistant material in fields such as the electrical and electronic industries, the universe, and the aerospace industry. Hardened material and formed body. Furthermore, the present invention provides an optical member and an optical lens which are excellent in optical characteristics such as high refractive index and which can impart high heat resistance and dimensional stability.

The inventors of the present invention have found that a benzyl ether compound having a bis(meth)acrylinyl group terminal having a bisphenol fluorene skeleton having a large planar structure and a curved portion is effective for solving the above problems, and thus completed the present invention.

That is, the present invention is an aromatic dihalomethyl compound represented by the following formula (1).

(wherein, Ar ¹ represents an aromatic hydrocarbon group having 6 to 50 carbon atoms, X represents a halogen element, n represents a number of 1 to 10, and R ¹ and R ² independently represent a hydrocarbon group having 1 to 50 carbon atoms; and p and q are independently The ground represents an integer from 0 to 2.)

Further, the present invention is a double (A) represented by the following formula (2) a benzyl ether compound at the end of the acrylonitrile group.

(In the formula (2), Ar ¹ represents an aromatic hydrocarbon group having 6 to 50 carbon atoms, Y represents hydrogen or a methyl group, n represents a number of 1 to 10, and R ¹ and R ² independently represent a hydrocarbon group having 1 to 50 carbon atoms. ;p, q independently represent an integer from 0 to 2).

Furthermore, the present invention is a process for producing a benzyl ether compound at the terminal of the bis(meth)acrylonitrile group, which comprises the above-mentioned aromatic dihalomethyl compound and (methyl) represented by the following formula (4) The acrylic compound reacts.

(wherein Y represents hydrogen or a methyl group, and Z represents hydrogen, an alkali metal, or a (meth)acrylonitrile group).

Furthermore, the present invention is a curable resin composition comprising a benzyl ether compound having a bis(meth)acrylonyl group terminal represented by the above formula (1) and a polymerization initiator.

Further, the present invention is to form the above curable resin composition into A curable film formed into a film shape and a film obtained by hardening it. Further, the present invention is a cured product obtained by curing the curable resin composition. Further, the present invention is a curable composite material composed of the above-mentioned curable resin composition and a substrate, and a cured composite material obtained by curing the cured composite material.

Further, the present invention is an optical article made of the above cured product and an optical lens.

The benzyl ether compound having a bis(meth)acrylonyl end group having a bisphenol fluorene skeleton having a large planar structure and a curved portion of the present invention can be used as a curable compound to have a large molecular size in a molecule. The free volume and the low polar group cause a high degree of low dielectric constant hardening. In addition, not only high flame retardancy and heat resistance, but also materials having a small dielectric constant and dielectric tangent, and excellent optical properties including high refractive index and high heat resistance and dimensional stability can be obtained. material.

The curable composition of the benzyl ether compound containing a bis(meth)acryl oxime group of the present invention exhibits excellent chemical resistance, dielectric properties, low water absorption, heat resistance, flame retardancy, and the like after curing. It is used as a dielectric material, an insulating material, a heat-resistant material, a structural material, etc. in the fields of the electrical industry, the universe, and the aerospace industry. In particular, it can be used as a single-sided, double-sided, multilayer printed substrate, a flexible printed substrate, a build-up substrate, or the like.

In addition, since the optical member and the optical lens of the present invention are excellent in optical characteristics including high refractive index, and have high heat resistance and dimensional stability, an optical pickup which is an imaging and recording medium for a compact camera can be used. Optical systems such as display devices, illumination devices, photocopying devices, and printing devices, glasses, contact lenses, and the like.

Fig. 1 is a GPC chart showing the aromatic bischloromethyl compound A of the present invention.

Fig. 2 is a GPC chart showing the aromatic bischloromethyl compound B of the present invention.

The invention is further illustrated below.

In the aromatic dihalomethyl compound represented by the formula (1) of the present invention, the production method is not particularly limited, but it is preferred to synthesize an aromatic crosslinking agent by reacting with a bisphenol quinone compound. As the aromatic crosslinking agent, a compound capable of imparting a crosslinking group represented by -CH2-Ar ₁ -CH2- may be used, and a dihalomethyl compound or a bismethylmethyl compound may be used, and a dihalomethyl compound is preferred. Hereinafter, the dihalomethyl compound represents an aromatic crosslinking agent, but when it is distinguished from the aromatic dihalomethyl compound of the formula (1), this is called a dihalomethyl group or an aromatic dihalo-methyl group. Base class.

In the present specification, the same symbols have the same meanings unless otherwise stated. Further, bis (methyl) benzyl ether compound of the group-terminated Bing Xixi benzyl, lines mean the formula ⁽¹⁾ Ar 1 -CH2 unit, typically not limited to benzyl.

Ar ¹ in the formula (1) is an aromatic hydrocarbon group having 6 to 50 carbon atoms and is a structural unit derived from an aromatic crosslinking agent. When the aromatic cross-linking agent is an aromatic dihalomethyl group, for example, an aromatic dihalomethyl group represented by the following formula (3) is preferable, but it is not limited thereto.

[Chemical Formula 4] ^{_{X-CH 2 -Ar 1 -CH 2}} -X (3) ( in the formula, Ar ¹ and X in the formula (1) is synonymous)

Specific examples of Ar ^1, is preferably selected from the group consisting of -Ph -, - Ph-Ph - , - Np -, - Np-CH 2 -Np -, - Ph-CH 2 -Ph -, - Ph-C (CH 3 ₂ -Ph-, -Ph-CH(CH ₃ )-Ph-, -Ph-CH(C ₆ H ₅ )-Ph-, -Ph-Flu-Ph-, and -Flu(CH ₃ ) ₂ - The aromatic hydrocarbon group having 6 to 50 carbon atoms in the group is particularly preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms. Here, Ph represents a phenyl group (-C ₆ H ₄ -), Np represents an anthranyl group (-C ₁₀ H ₆ -), and Flu represents a thiol group. Here, Ph, Np and Flu may have a substituent such as an alkyl group, an alkoxy group or a phenyl group. It is preferably an alkyl group having 1 to 6 carbon atoms. Particularly preferred are unsubstituted, methyl substituted and dimethyl substituted -Ph-Ph- and -Ph-. X represents a halogen element, and from the viewpoint of ease of industrial implementation, a halogen element selected from chlorine, bromine and iodine is preferably used, and chlorine is particularly preferred.

In the formula (1), n represents a number from 1 to 10, and when it has a molecular weight distribution, it is an average value (number average).

More specifically, the aromatic dihalomethyl group represented by the above formula (3) is exemplified by p-dichloromethylbenzene, m-dichloromethylbenzene, p-dibromomethylbenzene, m-dibromomethylbenzene. , 4,4'-bischloromethylbiphenyl, 4,3'-bischloromethylbiphenyl, 3,3'-bischloromethylbiphenyl, 2,2'-dichloromethylbiphenyl, 4 , 4'-bisbromomethylbiphenyl, 4,3'-bisbromomethylbiphenyl, 3,3'-bisbromomethylbiphenyl, 2,2'-dibromomethylbiphenyl, 1,4 -Dichloromethylnaphthalene, 1,5-dichloromethylnaphthalene, 1,6-dichloromethylnaphthalene, 2,3-dichloromethylnaphthalene, 2,4-dichloromethylnaphthalene, 2,5 - bischloromethylnaphthalene, 2,6-dichloromethylnaphthalene, 2,7-dichloromethylnaphthalene, 1,4-dibromomethylnaphthalene, 1,5-dibromomethylnaphthalene, 1,6 -dibromomethylnaphthalene, 2,3-dibromomethylnaphthalene, 2,4-dibromomethylnaphthalene, 2,5-dibromomethylnaphthalene, 2,6-dibromomethylnaphthalene, 2,7 - bisbromomethylnaphthalene, 9,9-bischloromethyl hydrazine, 9,9-bisbromomethyl hydrazine, 2,7-dichloromethyl hydrazine, 2,7-dichloromethyl-9,9- Dimethyl hydrazine, 2,7-dichloromethyl-9,9-diethyl fluorene, 2,7-dichloromethyl-9,9-di-n-propyl fluorene, 2,7-dichloromethyl -9,9-diisopropyl fluorene, 2,7-dichloromethyl-9,9-di-n-butyl fluorene, 2,7-dichloromethyl-9,9- Isobutyl hydrazine, 2,7-dichloromethyl-9,9-di(secondary butyl) fluorene, 2,7-dichloromethyl-9,9-di(tertiary butyl) fluorene, 2 ,7-dibromomethylhydrazine, 2,7-dibromomethyl-9,9-dimethylindole, 2,7-dibromomethyl-9,9-diethylanthracene, 2,7-double Bromomethyl-9,9-di-n-propyl fluorene, 2,7-dibromomethyl-9,9-diisopropyl fluorene, 2,7-dibromomethyl-9,9-di-n-butyl Bismuth, 2,7-dibromomethyl-9,9-diisobutylphosphonium, 2,7-dibromomethyl-9,9-di(secondary butyl) fluorene, 2,7-dibromo Base-9,9-di(tributyl)anthracene, 2,7-diiodomethylhydrazine, 2,7-diiodomethyl-9,9-dimethylindole, 2,7-diiodomethyl Base-9,9-two Base, 2,7-diiodomethyl-9,9-di-n-propyl fluorene, 2,7-diiodomethyl-9,9-diisopropyl hydrazine, 2,7-diiodomethyl- 9,9-di-n-butyl fluorene, 2,7-diiodomethyl-9,9-diisobutyl fluorene, 2,7-diiodomethyl-9,9-di(secondary butyl) fluorene , 2,7-diiodomethyl-9,9-di(tributyl)anthracene, 9,9-bis(4-chloromethylphenyl)anthracene, 9,9-bis(3-chloromethyl Phenyl)phosphonium, 9,9-bis(2-chloromethylphenyl)fluorene or the like, but is not limited thereto. Particularly preferred are p-dichloromethylbenzene, m-dichloromethylbenzene, p-dibromomethylbenzene, m-dibromomethylbenzene, 4,4'-dichloromethylbiphenyl, 4,3'-dichloro Methylbiphenyl, 3,3'-bischloromethylbiphenyl, 2,2'-bischloromethylbiphenyl, 4,4'-dibromomethylbiphenyl, 4,3'-dibromomethyl Biphenyl, 3,3'-bisbromomethylbiphenyl and 2,2'-bisbromomethylbiphenyl, and such methyl-substituted and dimethyl-substituted.

In the formula (1), p and q each independently represent an integer of 0 to 2. R ¹ and R ² each independently represent a hydrocarbon group having 1 to 50 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, particularly preferably an alkyl group having 1 to 12 carbon atoms. base.

A bisphenol oxime compound which reacts with an aromatic crosslinking agent, and is a compound represented by the following formula (5).

(wherein R ¹ , R ² , p, q have the same meanings as in formula (1))

More specifically, the bisphenol oxime compound represented by the formula (5) is exemplified by 9,9-bis(4-hydroxyphenyl)fluorene; 9,9-bis(4-hydroxy-2-methylphenyl) ), 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-bis(4-hydroxy-3-ethylphenyl)anthracene, 9,9-bis(4-hydroxyl) 9,9-bis(alkylhydroxyphenyl)anthracene of -3-tertiary butylphenyl)anthracene; 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9 9, 9-bis(4-hydroxy-2,6-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-di(tri-butyl)phenyl)anthracene, etc. 9-bis(dialkylhydroxyphenyl)anthracene; 9,9-bis(cycloalkylhydroxyphenyl)anthracene 9,9,9-bis(4-hydroxy-3-cyclohexylphenyl)anthracene; 9,9-bis(arylhydroxyphenyl)fluorene or the like such as 9-bis(4-hydroxy-3-phenylphenyl)fluorene, but is not limited thereto. Preferred is 9,9-bis(4-hydroxyphenyl)anthracene; 9,9-bis(4-hydroxy-2-methylphenyl)anthracene, 9,9-bis(4-hydroxy-3-methyl) Phenyl) ruthenium, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene.

The aromatic dihalomethyl compound of the formula (1) of the present invention is preferably synthesized by reacting an aromatic dihalomethyl group with a bisphenol fluorene compound of the formula (5) (step A).

In the step A, the use ratio of the aromatic dihalomethyl group of the formula (3) to the bisphenol fluorene-based compound of the formula (5) is preferably in an equivalent ratio (halogen ratio of halomethyl group: OH). 100:20~100:99. When it is in this range, the total amount of the bisphenol quinone-based compound is reacted with the aromatic dihalomethyl group to form a single halomethyl group in the aromatic dihalomethyl group remaining at both ends. Body or oligomer. Further, by controlling the above equivalent ratio, the number of n can be controlled. The value of n is 1 to 10, more preferably 1.2 to 10, more preferably 1.2 to 8, and particularly preferably 1.2 to 5. n is usually the average. In the present specification, the average value means the number average.

In this step A, in order to promote the reaction of the bisphenol fluorene-based compound with the aromatic dihalomethyl compound, the reaction can be carried out in the presence of an alkali metal hydroxide.

Next, a benzyl ether compound (hereinafter also referred to as a benzyl ether compound of the formula (2) or a benzyl ether compound of the present invention) represented by the formula (2) of the present invention will be described. The method for producing the benzyl ether compound at the terminal of the bis(meth)acrylonitrile group is not particularly limited, but is preferably represented by the aromatic dihalomethyl compound represented by the formula (1) and the formula (4). Synthesis of an acrylic compound. In the formula (4), Z represents hydrogen, an alkali metal, or a (meth)acrylonitrile group (CH ₂ =C(Y)-C(O)-), and Y has the same meaning as the formula (2).

In the production of the benzyl ether compound of the present invention, the aromatic dihalomethyl compound represented by the formula (1) obtained in the step A and the compound imparting the (meth) acrylate group are reacted industrially. More favorable. This reaction step was changed to step B. The aromatic dihalomethyl compound represented by the formula (1) is also referred to as an intermediate because it is used as an intermediate of the benzyl ether compound of the present invention.

As the (meth)acrylic compound represented by the formula (4), methacrylic acid, acrylic acid, methacrylic anhydride, acrylic anhydride, and the like or a mixture thereof may be used. Further, in the case of an alkali metal (meth)acrylate, the reaction proceeds more easily. In this case, it may be lithium (meth)acrylate, potassium (meth)acrylate or sodium (meth)acrylate.

In formula (4), when Z is a K (meth)acrylic acid When a compound such as potassium (meth)acrylate is used, potassium (meth)acrylate can be prepared by saponification of (meth) acrylate or neutralization of (meth)acrylic acid by potassium carbonate. In the case of the aforementioned neutralization, potassium carbonate is preferably excessive with respect to (meth)acrylic acid. At this time, potassium (meth)acrylate may not be separated from the reaction between the aromatic dihalomethyl compound and potassium (meth)acrylate. Excess alkali can promote the reaction.

The reaction of the aromatic dihalomethyl compound of the formula (1) in the step B and the (meth)acrylic compound of the formula (4) is not particularly limited, and for example, neutralization of Z with potassium carbonate in a polar solvent is exemplified. a (meth)acrylic acid of H to prepare a potassium salt, reacting the potassium salt with an aromatic dihalomethyl compound, and separating the alkali metal chloride of the by-product formed by filtration, thereby obtaining the purpose A method of bis(methyl)acrylonitrile terminated benzyl ether compound.

The ratio of the aromatic dihalomethyl compound to the (meth)acrylic compound is preferably from 100:95 to 100:120 in an equivalent ratio (halogen ratio of halomethyl:(meth)acrylonitrile group). , especially good for 100:100~100:110. When the equivalent ratio is in the range, the total amount of the aromatic dihalomethyl compound to be charged is reacted with the acrylic compound to form a halomethyl group in the aromatic dihalomethyl compound (methyl group). Acrylate, and hardly remains in the reactants, whereby when used as a curable resin composition, the hardening reaction can be sufficiently performed, and good dielectric properties are exhibited, and thermal stability is exhibited. It is also good, so it is better.

When carrying out the reaction of step B, a polar solvent can be used. Examples of preferred polar solvents include alcohols such as methanol, ethanol, propanol and butanol, and guanamine solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. An ether solvent such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxypropane or 1,2-dimethoxyethane, acetone, methyl ethyl ketone, methyl isobutyl ketone, or ring A ketone solvent such as ketone or the like, dimethyl hydrazine, acetonitrile or the mixed solvent.

In carrying out the reaction of the step B, a method of promoting the reaction by saponifying or neutralizing M of the acrylic compound of the formula (4) to form a salt of an alkali metal is preferably used. Preferred examples of the alkali metal salt include lithium (meth)acrylate, potassium (meth)acrylate, or sodium (meth)acrylate, and mixtures thereof. The ratio of the acrylate or the acrylic compound to the compound in the case of forming an alkali metal salt is preferably in the range of 1.05 to 2.0 times in terms of an equivalent ratio.

The reaction temperature and the reaction time in the step B can be appropriately selected depending on the reaction, and if the reaction is in the range of 30 to 100 ° C for 0.5 to 20 hours, the reaction can be sufficiently carried out.

By the above reaction, a benzyl ether compound of a bis(meth)acrylinyl group represented by the formula (3) can be obtained. The benzyl ether compound at the terminal of the bis(meth)acrylonitrile group obtained by the reaction can be further purified by reprecipitation purification or recrystallization to reduce the content of impurities.

The bis(meth)acrylonitrile-terminated benzyl ether compound of the present invention has two (meth)acrylonium groups and is used as a resin material, and is particularly useful as a resin composition for thermosetting resins. Monomer of matter.

The resin composition preferably contains a benzyl ether compound of a bis(meth)acryl oxime group and a polymerization initiator as essential components. The polymerization initiator may be a polymerization initiator which is generally used as a polymerization initiator of a vinyl compound, and may be applied to an active energy ray irradiation or a radical polymerization initiator of ultraviolet rays, electron beams or the like, but A free radical polymerization initiator (also known as a free radical polymerization catalyst).

The resin composition containing the benzyl ether compound of the bis(meth)acryl oxime group of the present invention is also called a curable resin composition because of its curability. The cured product obtained by curing the curable resin composition can be used as a molded product, a laminate, an injection molded article, an adhesive, a coating film, and a film. For example, the cured product of the semiconductor sealing material is an injection molded article or a molded product, and a method of obtaining a cured product for the purpose can be injection molded, or formed by using a transfer molding machine, an injection molding machine, a compression molding machine, or the like. And further heating at 80 to 230 ° C for 0.5 to 10 hours to obtain a cured product. Further, in the curable resin composition, an active energy ray irradiation device can be used to irradiate an active energy ray to obtain a cured product.

The curable resin composition containing the benzyl ether compound of the bis(meth)acryl oxime group of the present invention is cured by the above-described curing method to obtain a cured product suitable as an optical component. Such a suitable material for use as an optical component can be an optical article excellent in various optical characteristics, such as an optical lens.

Next, the curable composition of the present invention will be described.

The curable composition of the present invention contains a benzyl ether compound of a bis(meth)acrylonyl group represented by the formula (1) and a polymerization initiator. polymerization The initiator may be a polymerization initiator which is generally used as a polymerization initiator of a vinyl compound, and may be applied to an active energy ray irradiation or a radical polymerization initiator of ultraviolet rays, electron beams or the like, but is preferably used. It is a radical polymerization initiator (also known as a radical polymerization catalyst).

The radical polymerization initiator, for example, the resin composition of the present invention is hardened by a crosslinking reaction by heating or activation of an energy ray or the like as described later, but at this time, the reaction temperature is lowered or the unsaturated group is promoted. The crosslinking reaction initiator contains a radical polymerization initiator for the purpose. The amount of the radical polymerization initiator used for the purpose is 0.1 to 10% by weight, preferably 0.1 to 8% by weight based on the benzyl ether compound at the bis(meth)acryl oxime group. Since the radical polymerization initiator is a radical polymerization catalyst, the following is represented by a radical polymerization initiator.

Representative examples of the radical polymerization initiator which causes a crosslinking reaction by heating are benzamidine peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-di Hydrogen peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di(tertiary butyl peroxide), tertiary butyl cumene peroxide , α,α'-bis(tri-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(tri-butylperoxy)hexane, two Cumene hydroperoxide, di(tertiary butylperoxy) isophthalate, tert-butyl peroxybenzoate, 2,2,-bis(tertiary butylperoxy)butane , 2,2,-bis(tertiary butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, bis(trimethyldecane) peroxide And a peroxide such as a trimethylsulfonyltriphenylphosphonium peroxide, but is not limited thereto. In addition, although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane may also A radical polymerization initiator (or a polymerization catalyst) for promoting a crosslinking reaction by heating is used.

On the other hand, a representative example of a radical polymerization initiator which promotes a crosslinking reaction by irradiating an activation energy ray such as an ultraviolet ray or an electron beam is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin Benzoin such as isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1- Dichloroacetophenone, 2-mercapto-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4 Acetophenones such as -(methylthio)phenyl]-2-morpholinpropan-1-one; 2-ethylhydrazine, 2-tributylphosphonium, 2-chloroindole, 2- Anthraquinones such as amyl guanidine; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; acetophenone dimethyl condensate Acetals such as aldehydes, benzyl dimethyl acetals, etc.; diphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 4,4'-bismethylaminodiphenyl Diphenyl ketones such as ketones; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine Phosphine oxides such as oxides Wait. These may be used singly or as a mixture of two or more kinds, and may also be a tertiary amine such as triethanolamine or methyldiethanolamine, ethyl N,N-dimethylaminobenzoate, or N,N-di An accelerator such as a benzoic acid derivative such as isoamyl methylaminobenzoate is used in combination, but is not limited thereto.

The amount of the radical polymerization initiator to be added is not in the range of 0.01 to 10 parts by weight based on the benzyl ether compound at the end of the bis(meth)acryl oxime group, and is not caused by the oxygen dissolved in the resin composition. Block hardening The reaction allows the reaction to proceed well.

Further, in the curable composition of the benzyl ether compound containing a bis(meth)acryl oxime group, a benzyl ether compound capable of copolymerizing with the bis(meth)acryl oxime group of the present invention may be blended as necessary. Other polymerizable monomers are hardened.

Copolymerizable polymerizable monomer, which is styrene, styrene dimer, α-methylstyrene, α-methylstyrene dimer, divinylbenzene, vinyl toluene, tert-butyl Styrene, chlorostyrene, dibromostyrene, vinylnaphthalene, vinylbiphenyl, decene, divinylbenzyl ether, allyl phenyl ether, 1,4-butanediol di(meth)acrylate 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, di(meth)acrylic acid Bisphenol A polyethoxylate, bisphenol A dipropyl (meth)acrylate, bisphenol (poly) ethoxylate, ethylene glycol di(meth)acrylate, (methyl) Trimethylolpropane triethoxyethyl acrylate, tris(2-hydroxyethyl)trimeric isocyanate tris(meth)acrylate, neopentyl glycol tri(meth)acrylate, neopentyl tetra(meth)acrylate Alcohol ester, polyethylene glycol di(meth)acrylate, tris(propyleneoxyethyl) isocyanate, neopentyl tetra(meth)acrylate, dipentyne hexa(meth)acrylate Ε-hexyl ester of tetraol ester and neopentyl glycol hydroxypivalate Diester (meth) acrylate (for example, manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220, HX-620, etc.), trimethylolpropane tris(meth)acrylate, tris(methyl) ) Trimethylolpropane acrylate polyethoxylate, bis(trimethylolpropane) tetra(meth)acrylate, propylene fluorenyl Morpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, single Poly(propylene glycol) methyl acrylate, cyclohexane-1,4-dimethyl methacrylate, tetrahydrofuran (meth) acrylate, phenoxyethyl (meth) acrylate, benzene (meth) acrylate Polyethoxylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, o-phenylphenol monoethoxylate (meth)acrylate, o-phenylphenol poly(oxy)(meth)acrylate Ester, p-cumylphenoxyethyl (meth)acrylate, isodecyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (A) A monomer such as dicyclopentenyl acrylate or dicyclopentene oxyethyl (meth)acrylate.

Further, in the curable resin composition of the present invention, a known thermosetting resin such as a vinyl ester resin, a polyvinyl benzyl resin, an unsaturated polyester resin, a maleimide resin, or a ring may be used. Oxygen resin, polycyanate resin, phenol resin, etc., or known thermoplastic resins such as polystyrene, polyphenylene ether, polyetherimine, polyether oxime, PPS resin, polycyclopentadiene resin a polycycloolefin resin or the like, or a known thermoplastic elastomer such as a styrene-ethylene-propylene copolymer, a styrene-ethylene-butene copolymer, a styrene-butadiene copolymer, a styrene-different A pentadiene copolymer, a hydrogenated styrene-butadiene copolymer, a hydrogenated styrene-isoprene copolymer, or the like, or a rubber such as polybutadiene or polyisoprene may be blended together.

In the curable resin composition of the present invention, by using molten cerium oxide, crystalline cerium oxide, aluminum oxide, cerium nitride, aluminum nitride Inorganic fillers, non-flammability imparting agents such as decabromodiphenylethane and brominated polystyrene, etc., may be particularly useful for use as electrical or electronic parts requiring dielectric properties or flame retardancy or heat resistance. Materials, especially varnishes for semiconductor sealing materials or circuit boards.

The varnish for a circuit board material can be produced by dissolving the curable resin composition of the present invention in a solvent such as toluene, xylene, tetrahydrofuran or dioxolane. Specific examples of the circuit board material include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.

The cured product obtained by curing the curable resin composition of the present invention can be used as a molded product, a laminate, an injection molded article, an adhesive, a coating film, and a film. For example, the cured product of the semiconductor sealing material is an injection molded article or a molded product, and a method of obtaining a cured product for the purpose can be injection molded, or formed by using a transfer molding machine, an injection molding machine, a compression molding machine, or the like. And further heating at 80 to 230 ° C for 0.5 to 10 hours to obtain a cured product. In the curable resin composition of the present invention, an active energy ray irradiation device can be used to irradiate an active energy ray to obtain a cured product. Here, examples of the light source used when the active energy ray is irradiated and hardened include, for example, a xenon lamp, a carbon arc lamp, a germicidal lamp, a fluorescent lamp for ultraviolet light, a high pressure mercury lamp for photocopying, a medium pressure mercury lamp, and a high voltage. A mercury lamp, an ultra-high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or an electron beam formed by a scanning type or a 电子-type electron beam acceleration path. Further, when the curable resin composition of the present invention is cured by ultraviolet irradiation, the amount of ultraviolet irradiation required for curing may be approximately 300 to 40,000 mJ/cm ² . In order to sufficiently harden the resin composition, it is preferred to irradiate an active energy ray such as ultraviolet rays in an inert gas atmosphere such as nitrogen.

Further, the cured product of the varnish for a circuit board is a laminate, and the cured product is obtained by impregnating the circuit board with a varnish in glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, or the like. The substrate is heated and dried to obtain a prepreg, and laminated separately or laminated with a metal foil such as copper foil, and then obtained by hot press molding.

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

In addition, the curable resin composition of the present invention can be used in the same manner as the hardened composite material described later, and can be bonded to a metal foil (which is the same as the metal plate, the same applies hereinafter).

Next, the curable composite material of the curable resin composition of the present invention and a cured body thereof will be described. In the curable composite material composed of the curable resin composition of the present invention, a base material is added in order to improve mechanical strength and increase dimensional stability.

Such a substrate is provided with various glass cloths, asbestos cloths, metal fiber cloths and other synthetic or natural inorganic fiber cloths such as yarn bundle cloth, cloth, stranded felt, surface felt, etc.; from wholly aromatic polyamide fibers, all a woven or non-woven fabric obtained from a liquid crystal fiber such as an aromatic polyester fiber or a polybenzoxazole fiber; a woven or non-woven fabric obtained from a synthetic fiber such as polyvinyl alcohol fiber, polyester fiber or acrylic fiber; Natural fiber cloth such as linen, fiber mat, carbon fiber cloth, kraft paper, cotton paper, paper-glass hybrid fiber A cloth such as a natural cellulose-based cloth such as a crepe paper, a paper, or the like may be used alone or in combination of two or more.

The ratio of the substrate is 5 to 90% by weight, preferably 10 to 80% by weight, more preferably 20 to 70% by weight in the curable composite material. When the substrate is less than 5% by weight, the dimensional stability or strength of the composite material after hardening is insufficient, and further, when the substrate is more than 90% by weight, the dielectric properties of the composite material are deteriorated, which is not preferable.

In the curable composite material of the present invention, a coupling agent can be used for the purpose of improving the adhesion at the interface between the resin and the substrate as necessary. As the coupling agent, a general use of a decane coupling agent, a titanate coupling agent, an aluminum coupling agent, an aluminum zirconium coupling agent or the like can be used.

In the method of producing the curable composite material of the present invention, for example, the curable resin composition of the present invention and other components as necessary are uniformly dissolved or dispersed in the aromatic solvent, the ketone solvent or the like or a mixed solvent thereof. And drying the method after impregnating the substrate. Impregnation can be carried out by dipping (soaking), coating, or the like. The impregnation may be repeated as many times as necessary. Further, at this time, the impregnation may be repeated using a plurality of solutions having different compositions or concentrations, and finally adjusted to a desired resin composition and resin amount.

The hardenable composite material of the present invention is cured by a method such as heating, whereby a hardened composite material can be obtained. The production method is not particularly limited. For example, a plurality of sheets of the curable composite material may be laminated, and the layers may be adhered to each other under heat and pressure while being thermally hardened to obtain a hardened composite material having a desired thickness. In addition, it is also possible to combine hardened hardened composite materials with hard A composite material is obtained to obtain a hardened composite material composed of a new layer. The layer formation and hardening are usually carried out simultaneously using hot molding or the like, but the two can also be carried out separately. That is, the uncured or semi-hardened composite material obtained by performing the layer formation in advance may be cured by heat treatment or other methods.

The curing and hardening of the curable composite material of the present invention can be carried out at a temperature of 80 to 300 ° C, a pressure of 0.1 to 1000 kg/cm ² , a time of 1 minute to 10 hours, preferably a temperature of 150 to 250 ° C, Pressure: 1 to 500 kg/cm ² , time: 1 minute to 5 hours.

The laminate containing the curable resin composition of the present invention is composed of a layer of the cured composite material of the present invention and a layer of a metal foil. Examples of the metal foil used herein include a copper foil, an aluminum foil, and the like. The thickness is not particularly limited and may be in the range of 3 to 200 μm, and more preferably in the range of 3 to 105 μm.

The method of producing the laminate containing the curable resin composition of the present invention, for example, laminates the curable property obtained from the curable resin composition of the present invention and the substrate described above in accordance with the layer constitution of the purpose. The composite material, as well as the metal foil, is then adhered between the layers under heat and pressure while simultaneously performing thermal hardening. In the laminate of the curable resin composition of the present invention, the hardened composite material and the metal foil may be laminated by any layer constitution. Metal foil can be used as the skin or intermediate layer. In addition to the above, a plurality of laminations and hardening may be repeated to form a multilayer.

Adhesive can also be used for adhesion to metal foil. Examples of the adhesive include epoxy, acrylic, phenol, and cyanoacrylate, but It is not particularly limited to this. The above-mentioned layer formation and hardening can be carried out under the same conditions as in the production of the hardened composite material of the present invention.

The film obtained from the curable resin composition of the present invention is a cured film in which the curable resin composition of the present invention is formed into a film-like curable film and cured. The thickness is not particularly limited and may be in the range of 3 to 200 μm, and more preferably in the range of 5 to 105 μm.

The method of producing the film of the present invention is not particularly limited, and for example, the curable resin composition and other components necessary for the preparation are uniformly dissolved or dispersed in a solvent such as an aromatic or ketone system or a mixed solvent thereof, and coated. A method of drying after coating a resin film such as a PET film. The coating may be repeated as many times as necessary. Further, in this case, the coating may be repeated using a plurality of solutions having different compositions or concentrations, and finally adjusted to a desired resin composition and resin amount. A hardenable film that can be hardened before or after application depending on the application.

The resin-attached metal foil using the curable resin composition of the present invention is composed of the curable resin composition of the present invention and a metal foil. Examples of the metal foil used herein include a copper foil, an aluminum foil, and the like. The thickness is not particularly limited and may be in the range of 3 to 200 μm, and more preferably in the range of 5 to 105 μm.

The method of producing the resin-attached metal foil using the curable resin composition of the present invention is not particularly limited, and for example, the curable resin composition and other components necessary for the preparation are uniformly dissolved or dispersed in the aromatic system. A method in which a solvent such as a ketone system or a mixed solvent thereof is applied to a metal foil and then dried. Coating can be repeated as necessary In addition, at this time, it is also possible to repeat the coating using a plurality of solutions having different compositions or concentrations, and finally adjust to the desired resin composition and resin amount.

The method of producing an optical article and an optical lens by curing the curable resin composition containing the benzyl ether compound of the bis(meth)acryl fluorenyl group of the present invention can be preferably used by heating or activation of energy rays. The method of the resin composition can be appropriately selected depending on the type of the resin composition, but it is preferably a method of curing the curable resin composition within 5 minutes to produce a cured product. Specifically, it is preferred to apply the mixed liquid to a mold having a shape of a cured product, and to cure the curable resin composition within 5 minutes. By using a mold for hardening in a short time, it is an economically excellent method. In this manner, the curable resin composition is cured to produce an optical article and an optical lens.

When the above hardening time (hardening time using a mold) exceeds 5 minutes, productivity is deteriorated. It is preferably less than 3 minutes, more preferably less than 2 minutes, and most preferably less than 1 minute. When hardening by heating, the hardening temperature can be appropriately set in accordance with the cured resin composition or the like, and is preferably 80 to 250 °C. It is preferably 100 to 220 ° C, more preferably 120 to 200 ° C. The curable resin composition containing the benzyl ether compound of the bis(meth)acryl oxime group of the present invention may be obtained by irradiating an active energy ray such as ultraviolet rays. Here, a specific example of the light source used when the curable energy ray such as ultraviolet rays is applied to the curable resin composition used for molding the optical article and the optical lens of the present invention is, for example, a xenon lamp or carbon. Pole arc lamp, germicidal lamp, ultraviolet fluorescent lamp, high pressure mercury lamp for photocopying, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, electrodeless lamp, metal halide lamp, or according to scanning type An electron beam or the like formed by an electron beam acceleration path. Further, when the resin composition of the present invention is cured by ultraviolet irradiation, the amount of ultraviolet irradiation required for hardening may be about 300 to 30,000 mJ/cm ² . In order to sufficiently harden the resin composition of the present invention, it is preferred to irradiate an active energy ray such as ultraviolet rays in an inert gas atmosphere such as nitrogen.

In the curable resin composition containing the benzyl ether compound of the bis(meth)acryl oxime group of the present invention, after hardening within 5 minutes using a mold as described above, it is preferred to remove the cured product from the mold for post-hardening. (bake). By performing post-hardening, the cured product can have sufficient hardness, and can be preferably used in various applications. Further, in the post-curing, the handleability is also good from the viewpoint of further curing the cured product to some extent. Therefore, since the mold can be omitted, there is an advantage that a large number of products can be post-hardened in a small area.

In the post-hardening, the hardening temperature and the hardening time can be appropriately selected in accordance with the cured resin composition or the like. For example, the hardening temperature is preferably from 80 to 200 °C. It is preferably 100 to 180 ° C, more preferably 110 to 150 ° C. Although the hardening time of the post-hardening depends on the hardening temperature, it is preferably from 1 to 48 hours. It is preferably 1 to 10 hours, more preferably 1 to 5 hours.

The curable resin composition containing the benzyl ether compound of the bis(meth)acryl oxime group of the present invention can obtain a cured optical article by the above-mentioned curing method, and the cured optical article becomes various optical specialties. Excellent optical articles and optical lenses. For example, the haze (haze) of the optical article using the curable resin composition containing the benzyl ether compound of the bis(meth)acryl oxime group of the present invention is preferably 2% or less. Thus, the resin composition using the curable resin composition containing the curable resin composition of the bis(meth)acryl fluorenyl terminal benzyl ether compound of the present invention having a haze of 2% or less is also a preferred embodiment of the present invention. One.

The turbidity of the cured optical article is preferably 2% or less, more preferably 2% or less, still more preferably 1% or less, and particularly preferably 0.7% or less. As the transparency, the light transmittance in the visible light region (the region having a wavelength of 450 to 780 nm) is preferably 85% or more. The light transmittance of the cured product is particularly preferably 87% or more, more preferably 88% or more, and particularly preferably 89% or more.

The use of the above optical article, specifically, a lens lens, a (digital) camera, a camera lens such as a mobile phone or a car camera, a filter, a diffraction grating, a cymbal, a light guide, a beam concentrating lens or Optical applications such as transparent glass or protective glass for lenses for light diffusion, viewing windows, and protective glass for display devices; optical sensors, optical switches, LEDs, light-emitting elements, optical waveguides, multiplexers, and demultiplexers Optical device use such as a device, a circuit breaker, a light splitter, or a fiber-optic adhesive; a substrate for a display element such as an LCD or an organic EL or a PDP, a substrate for a color filter, a substrate for a touch panel, a display protective film, and a display backlight , display devices such as light guide plates, anti-reflection films, and anti-fog films, etc.

[Examples]

The invention is illustrated by the following examples, but the invention It is not limited to this. The parts in each case are parts by weight. Further, in the measurement results in the examples, sample preparation and measurement were carried out by the method shown below.

1) GPC purity of aromatic dihalomethyl compound and benzyl ether compound at the end of bis(meth)acrylonitrile

The molecular weight and molecular weight distribution were measured by using GPC (HLC-8120GPC, manufactured by Tosoh Corporation) under the conditions of a solvent: tetrahydrofuran (THF), a flow rate of 1.0 ml/min, and a column temperature of 40 °C. It was calculated from the area ratio of each peak detected by a UV detector (wavelength: 254 nm). The molecular weight was measured using a calibration curve of monodisperse polystyrene and measured by the molecular weight of polystyrene.

2) Structure of aromatic dihalomethyl compound and benzyl ether compound at the end of bis(meth)acrylonitrile

The JNM-LA600 type nuclear magnetic resonance spectroscopic device manufactured by JEOL Ltd. was determined by ¹³ C-NMR and ¹ H-NMR analysis. The solvent used was chloroform-d ₁ . The resonance line of tetrachloroethane-d ₂ of the solvent was measured by NMR as an internal standard.

3) Viscosity

The measurement was carried out at a temperature of 25 ° C using an E-type viscometer.

4) Dielectric constant and dielectric tangent

The curable resin composition varnish was poured between two glass plates sandwiching a spacer having a thickness of 0.2 mm, and was irradiated with a UV irradiation device having a high-pressure mercury lamp at an irradiation intensity of 30 mW/cm ² and a UV irradiation amount: UV hardening was performed at 6,000 mJ/cm ² . Then, the flat plate sample obtained by UV hardening was post-baked in an oven at 200 ° C for 30 minutes, and the properties of the obtained cured plate were measured. In addition, a flat plate-shaped cured product having a thickness of 0.2 mm was cut into a size of 0.3 cm × 10 cm to prepare a test piece, and a dielectric constant measuring device made of a hole-resonator method manufactured by AET Co., Ltd. was used in absolute terms in accordance with JIS C2565. After drying at 23 ° C for 24 hours in a room with a humidity of 50%, the dielectric constant and dielectric tangent of 2.0 GHz were measured.

5) Modulation and measurement of test piece for measuring linear expansion coefficient (CTE) and glass transition temperature (Tg)

The curable resin composition was placed between two molds of a glass plate having a 200 μm-thick spacer made of ruthenium rubber, and an injection molded sample was produced, and the bubbles were removed under reduced pressure. Then, for the thermosetting sample, the injection molded sample was placed in an inert gas oven under a nitrogen gas stream, and the temperature was gradually increased in 15 minutes, followed by thermal hardening at 200 ° C for 60 minutes. On the other hand, for the UV-curable sample, UV curing was performed using a conveyor belt type UV irradiation device at a UV irradiation amount of 6,000 mJ/cm ² . For the thermosetting sample and the UV-curing sample, post-hardening was carried out at 200 ° C for 30 minutes under an air flow using an inert gas oven. A flat sample of 3 mm width was prepared from the obtained 200 μm-thick flat plate, and a test piece for CTE measurement (TMA method) and Tg measurement (DMA method) was used.

The CTE measurement (TMA method) is a test piece prepared by the above method, and is placed in an analysis probe of a TMA (thermomechanical analysis device) measuring device, and scanned at a temperature rising rate of 10 ° C / min from 30 ° C under a nitrogen gas stream. The measurement was carried out at 360 ° C, and the average linear expansion coefficient in the temperature range of 0 to 40 ° C was obtained.

On the other hand, the measurement of the hardened test piece produced by the above method was carried out at a temperature increase rate of 2 ° C/min using a dynamic viscoelasticity measuring device, and was determined from the peak value of the loss elastic modulus.

6) Determination of flame retardancy

In the case of producing a test piece for measuring a coefficient of linear expansion (CTE) and a glass transition temperature (Tg), a hardened sample sampled from the produced flat plate was used, and a TGA (heat scale) measuring device was used under a nitrogen gas flow. The measurement was carried out by scanning from 30 ° C to 600 ° C at a temperature increase rate of 10 ° C /min, and from the carbon (carbide) formation amount at 550 ° C, flame retardancy was determined as follows.

Flame retardant A: char production >40wt%

Flame retardant B: 25wt% < char production ≦ 40wt%

Flame retardant C: 18wt% < char production ≦ 25wt%

Flame retardancy D: 10wt% < char production ≦ 18wt%

Flame retardant E: carbon production ≦ 10wt%

7) Determination of YI, Haze and total light transmittance

YI, Haze, and total light transmittance were measured by flowing the prepared curable resin composition varnish into between two glass plates sandwiching a 1.0 mm thick spacer by UV irradiation with a high pressure mercury lamp. means an irradiation intensity: 30mW / cm ^2, UV irradiation amount: 6,000mJ / cm ² for UV curing. Then, the flat plate sample obtained by UV hardening was post-baked in an oven at 200 ° C for 30 minutes, and the obtained cured plate was measured using a turbidimeter and a color difference meter.

8) Determination of refractive index and Abbe number

The refractive index and the Abbe number are measured by flowing the prepared curable resin composition varnish into between two glass plates sandwiching a spacer having a thickness of 1.0 mm, and a UV irradiation device having a high-pressure mercury lamp is used. UV hardening was performed with an irradiation intensity: 30 mW/cm ² and a UV irradiation amount: 6,000 mJ/cm ² . Then, the flat plate sample obtained by UV hardening was post-baked in an oven at 200 ° C for 30 minutes to obtain a cured plate. The end surface of the obtained cured flat plate was subjected to mash processing, and dried in a vacuum desiccator at 60 ° C for 5 hours, and then placed in a tank of a thermo-hygrostat at 20 ° C and 60% RH for 2 days or more to carry out the state. Adjustment. The refractive index was measured at 25 ° C using a Karunyu refractometer KPR-2000 (manufactured by Shimadzu Device Co., Ltd.), and the Abbe number was calculated from the obtained refractive index data.

9) Formability

An uncured film of a curable resin composition laminated to a copper foil The surface of the copper foil after blackening treatment of the copper-clad laminate (copper layer/core layer=35 μm/300 μm) of the blackening treatment was carried out using a vacuum laminator at a temperature of 110 ° C and a molding pressure of 0.1. Vacuum lamination was carried out at MPa, and evaluation was carried out by blackening the adhesion state of the copper foil to the film. In the evaluation, the adhesion state of the copper foil and the film by the blackening treatment is "○", and the adhesion state in which the copper foil and the film are easily peeled off by the blackening treatment is "x".

Example 1

Adding 9,9-bis(4-hydroxyphenyl)fluorene 140.16 g (0.40 mol), 4,4'-bis(chloromethyl)biphenyl 141.40 g (0.88 mol), and acetone 1200 ml to the reaction vessel The temperature was raised to 78 ° C while stirring. Next, KOH-MeOH (KOH: 0.88 mol) was dropped into the reaction vessel maintained at 78 ° C for 30 minutes. After the completion of the dropwise addition, stirring was continued at 78 ° C for 4 hours. After 4 h, it was cooled to room temperature, 900 ml of toluene was added, and then 10% HCl was added for neutralization. Then, the aqueous phase was separated and separated, and the mixture was washed three times with 300 ml of water.

The organic phase obtained was concentrated by distillation, and methanol was added to reprecipitate the product. The precipitate is filtered and dried to obtain an aromatic dichloromethyl compound A of a reaction product of 9,9-bis(4-hydroxyphenyl)anthracene and 4,4'-bis(chloromethyl)biphenyl ( 2CM-DMBP-BPFZ) 169.33g. The obtained 2CM-DMBP-BPFZ was a white powder.

The product was confirmed by gel permeation chromatography (GPC), infrared spectroscopy (IR), and ¹ H nuclear magnetic resonance spectroscopy ( ¹ H-NMR). As a result, 1) from the GPC measurement results, it was found that the peak of the raw material disappeared in the recovered reaction product, and a new peak was generated on the high molecular weight side, and 2) the IR measurement result was known. The peak from the phenolic hydroxyl group was reduced, and 3) in the ¹ H-NMR measurement, it was confirmed that the resonance ray of the proton of the chloromethyl group derived from 4,4'-bis(chloromethyl)biphenyl was reduced, and instead A resonance ray from a proton of benzyl ether was formed in the vicinity of 5.02 ppm, and thus it was confirmed that an aromatic bischloromethyl compound A (2CM-DMBP-BPFZ) was obtained.

Fig. 1 is a GPC chart showing the GPC chart of 2,9-bis(4-hydroxyphenyl)fluorene of 2CM-DMBP-BPFZ and a raw material. 2CM-DMBP-BPFZ is indicated by a solid line, and 9,9-bis(4-hydroxyphenyl)anthracene is indicated by a broken line.

From the GPC elution curve of 2CM-DMBP-BPFZ in Fig. 1, the peak of 9,9-bis(4-hydroxyphenyl)fluorene of the starting material disappeared, and it was found that it shifted to the high molecular weight side.

The GPC purity (area ratio) of the component of nCM = 1 or more of 2CM-DMBP-BPFZ is as follows.

n=1 component: 7.8%

n=2 component: 27.2%

n=3 component: 30.6%

n=4 component: 18.2%

Composition with n=5 or more: 15.1%

Other ingredients (low molecular weight ingredients): 1.2%

Further, in the TGA measurement of 2CM-DMBP-BPFZ, an exothermic peak was observed at 220 ° C and 271 ° C in the differential thermal analysis (DTA) curve in the TGA measurement results. In addition, at 220 ° C 0.75 wt% was observed in the heat peak, and a weight loss of 4.88 wt% was observed in the exothermic peak at 271 °C. Further, the amount of carbide formation at 600 ° C was 62.2% by weight.

Example 2

9,9-bis(4-hydroxyphenyl)fluorene 140.16 g (0.40 mol), α,α'-dichloro-p-xylene 157.20 g (0.88 mol), and MEK 1200 ml were added to the reaction vessel while stirring. The temperature was raised to 78 ° C. Next, KOH-MeOH (KOH: 0.88 mol) was dropped into the reaction vessel maintained at 78 ° C for 30 minutes. After the completion of the dropwise addition, stirring was continued at 78 ° C for 4 hours. After 4 h, it was cooled to room temperature, 900 ml of toluene was added, and then 10% HCl was added for neutralization. Then, the aqueous phase was separated and separated, and the mixture was washed three times with 300 ml of water.

The organic phase obtained was concentrated by distillation, and methanol was added to reprecipitate the product. The precipitate was filtered and dried to obtain an aromatic dichloromethyl compound B (2CM-Xy) of a reaction product of 9,9-bis(4-hydroxyphenyl)phosphonium with α,α'-dichloro-p-xylene. -BPFZ) 123.57g.

The product was confirmed by gel permeation chromatography (GPC), infrared spectroscopy (IR), and ¹ H nuclear magnetic resonance spectroscopy ( ¹ H-NMR). As a result, 1) from the GPC measurement results, it was found that the peak of the raw material disappeared in the recovered reaction product, and a new peak was generated on the high molecular weight side, and 2) the IR measurement result was known. The peak from the phenolic hydroxyl group was decreased, and 3) in the ¹ H-NMR measurement, it was confirmed that the resonance ray of the proton of the chloromethyl group derived from α,α'-dichloro-p-xylene was reduced, and was replaced by 5.02 ppm. A resonance ray from a proton of benzyl ether was formed in the vicinity, and thus it was confirmed that an aromatic bischloromethyl compound B (2CM-Xy-BPFZ) was obtained.

Fig. 2 is a GPC chart showing the GPC chart of 2,9-bis(4-hydroxyphenyl)fluorene of 2CM-Xy-BPFZ and a raw material. 2CM-Xy-BPFZ is indicated by a solid line, and 9,9-bis(4-hydroxyphenyl)anthracene is indicated by a broken line.

From the GPC elution curve in Fig. 2, the peak of 9,9-bis(4-hydroxyphenyl)fluorene of the starting material disappeared, and it was found that it shifted to the high molecular weight side. Further, the GPC purity of the component of nCM or more of 2CM-Xy-BPFZ is as follows.

n=1 component: 36.3%

n=2 component: 28.5%

n=3 component: 19.6%

n=4 component: 10.6%

Composition with n=5 or more: 4.1%

Other ingredients (low molecular weight ingredients): 0.9%

When the TGA measurement of 2CM-Xy-BPFZ was carried out, an exothermic peak was observed at 219 ° C and 268 ° C in the differential thermal analysis (DTA) curve in the TGA measurement results. Further, 0.81% by weight was observed in the exothermic peak at 219 ° C, and a weight loss of 5.21% by weight was observed in the exothermic peak at 271 ° C. Further, the amount of carbide formation at 600 ° C was 57.8 wt%.

Example 3

Potassium carbonate 15.28g (0.11 mole) and N,N-dimethylformamide (DMF) 500 ml was added to the reaction vessel and heated and stirred. Once the internal temperature of the reaction vessel reached 80 ° C, a solution of 19.13 g (0.22 mol) of methacrylic acid dissolved in 50 ml of DMF was added dropwise over 30 minutes. This temperature was maintained to carry out a reaction for 1 hour. Next, a solution in which 2CM-DMBP-BPFZ 58.27 g obtained in Example 1 was dissolved in 500 ml of DMF was dropped over 30 minutes. After the completion of the dropwise addition, stirring was continued at 80 ° C for 3 hours. After 3 h, it was cooled to room temperature, and the solid precipitate was filtered. Then, 2000 ml of toluene was added to the reaction solution. Thereafter, the reaction solution was washed with water four times, and the oil phase was dried with magnesium sulfate and filtered. With respect to the obtained organic phase, the product was reprecipitated by a water/methanol mixed solvent.

The precipitate was filtered and dried to obtain 2MA-DMBP-BPFZ 52.64 g of a reaction product of 2CM-DMBP-BPFZ and methacrylic acid.

The product was confirmed by gel permeation chromatography (GPC), infrared spectroscopy (IR), and ¹ H nuclear magnetic resonance spectroscopy ( ¹ H-NMR). As a result, 1) from the GPC measurement results, it was found that the peak of the raw material disappeared in the recovered reaction product, and a new peak was generated on the high molecular weight side, and 2) the IR measurement result was known. When a carbonyl group was formed and a resonance ray having a proton derived from a methacrylic group was confirmed in ¹ H-NMR, 2MA-DMBP-BPFZ was confirmed.

Example 4

To the reaction vessel, 14.59 g (0.105 mol) of potassium carbonate and 500 ml of N,N-dimethylformamide (DMF) were added and heated and stirred. Once the internal temperature of the reaction vessel reaches 80 ° C, it will be 50 ml in DMF in 30 minutes. A solution in which 18.26 g (0.21 mol) of methacrylic acid was dissolved was dropped. This temperature was maintained to carry out a reaction for 1 hour. Then, a solution in which 2CM-Xy-BPFZ 62.76 g obtained in Example 2 was dissolved in 500 ml of DMF was added dropwise over 30 minutes. After the completion of the dropwise addition, stirring was continued at 80 ° C for 3 hours. After 3 h, it was cooled to room temperature, and the solid precipitate was filtered. Then, 2000 ml of toluene was added to the reaction solution. Thereafter, the reaction solution was washed with water four times, and the oil phase was dried with magnesium sulfate and filtered. With respect to the obtained organic phase, the product was reprecipitated by a water/methanol mixed solvent.

The precipitate was filtered and dried to obtain 2MA-Xy-BPFZ 69.53 g of a reaction product of 2CM-Xy-BPFZ and methacrylic acid.

The product was confirmed by gel permeation chromatography (GPC), infrared spectroscopy (IR), and ¹ H nuclear magnetic resonance spectroscopy ( ¹ H-NMR). As a result, 1) from the GPC measurement results, it was found that the peak of the raw material disappeared in the recovered reaction product, and a new peak was generated on the high molecular weight side, and 2) the IR measurement result was known. When a carbonyl group was formed and a resonance ray having a proton derived from a methacrylic group was confirmed in ¹ H-NMR, 2MA-Xy-BPFZ was confirmed.

Synthesis Example 1

231 g (epoxy equivalent 231) of bisphenol fluorene type epoxy resin, 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-diisobutylphenol, and 72.0 g of acrylic acid were placed in a 500 ml four-necked flask and mixed. The mixture was heated and dissolved at 90 to 100 ° C while blowing air at a rate of 25 ml per minute. Although the solution was cloudy, it slowly warmed up slowly and heated to 120 ° C to complete Dissolved. The solution gradually became transparent and viscous, but stirring was continued, and the acid value was measured therebetween, and heating and stirring were continued until the acid value became less than 2.0 mgKOH/g. It takes 8 hours until the acid value reaches the target (acid value of 0.8). Then, it was cooled to room temperature to obtain 243.6 g of a bisphenol fluorene type acrylate epoxy resin which was a colorless transparent solid.

Example 5

8 g of 2MA-DMBP-BPFZ obtained in Example 3 and o-phenyl-phenoxyethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester A-LEN-10) 12 g as a reactive diluent And 0.40 g of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184) as a photopolymerization initiator was mixed and dissolved to obtain a curable composition (varnish A).

The prepared varnish A was poured between two glass plates sandwiching a spacer having a thickness of 0.2 mm, and was irradiated with a UV irradiation device having a high-pressure mercury lamp at an irradiation intensity of 30 mW/cm ² and a UV irradiation amount of 6,000. UV hardening was performed at mJ/cm ² . Then, the flat plate sample obtained by UV hardening was post-baked in an oven at 200 ° C for 30 minutes, and the properties of the obtained cured plate were measured. Further, a flat plate-shaped cured product having a thickness of 0.2 mm was cut into 0.3 cm × 10 cm to prepare a test piece, and a dielectric constant and a dielectric tangent of 2.0 GHz were measured. The results obtained by these measurements are shown in Table 1.

Comparative example 1

8 g of bisphenol fluorene type acrylate epoxy resin obtained in Synthesis Example 1 and o-phenyl-phenoxyethyl acrylate as a reactive diluent (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester A-LEN -10) 12 g, and 0.40 g of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184) as a photopolymerization initiator were mixed and dissolved to obtain a curable composition (varnish B). .

The prepared varnish B was poured between two glass plates sandwiching a spacer having a thickness of 0.2 mm, and was irradiated with a UV irradiation device having a high-pressure mercury lamp at an irradiation intensity of 30 mW/cm ² and a UV irradiation amount of 6,000. UV hardening was performed at mJ/cm ² . Then, the flat plate sample obtained by UV hardening was post-baked in an oven at 200 ° C for 30 minutes, and the properties of the obtained cured plate were measured. Further, a flat plate-shaped cured product having a thickness of 0.2 mm was cut into 0.3 cm × 10 cm to prepare a test piece, and a dielectric constant and a dielectric tangent of 2.0 GHz were measured. The results obtained by these measurements are shown in Table 1.

In the table, the BPF resin is a bisphenol oxime type epoxy acrylate resin.

Example 6

To the reaction vessel, 15.28 g (0.11 mol) of potassium carbonate and 500 ml of N,N-dimethylformamide (DMF) were added and heated and stirred. Once the internal temperature of the reaction vessel reached 80 ° C, a solution of 15.85 g (0.22 mol) of acrylic acid dissolved in 50 ml of DMF was dropped over 30 minutes. This temperature was maintained to carry out a reaction for 1 hour. The aromatic dichloromethyl group of the reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and 4,4'-bis(chloromethyl)biphenyl was dissolved in 500 ml of DMF over 30 minutes. A solution of the compound (2CM-DMBP-BPFZ of Example 1) 58.27 g was added dropwise. After the completion of the dropwise addition, stirring was continued at 80 ° C for 3 hours. After 3 h, cool to room temperature and filter Body precipitates. Then, 2000 ml of toluene was added to the reaction solution. Thereafter, the reaction solution was washed with water four times, and the oil phase was dried with magnesium sulfate and filtered. With respect to the obtained organic phase, the product was reprecipitated by a water/methanol mixed solvent.

The precipitate was filtered and dried to obtain 49.87 g of 2A-DMBP-BPFZ as a reaction product of 2CM-DMBP-BPFZ and acrylic acid.

The product was confirmed by gel permeation chromatography (GPC), infrared spectroscopy (IR), and ¹ H nuclear magnetic resonance spectroscopy ( ¹ H-NMR), and it was confirmed from GPC that the reaction was recovered. The peak from the raw material disappeared, and a new peak was formed on the high molecular weight side. From the IR, it was confirmed that a carbonyl group was formed, and in ¹ H-NMR, a resonance ray having a proton derived from an acrylic group was confirmed. Therefore, it was confirmed that 2A-DMBP-BPFZ was obtained.

Example 7

To the reaction vessel, 14.59 g (0.105 mol) of potassium carbonate and 500 ml of N,N-dimethylformamide (DMF) were added and heated and stirred. Once the internal temperature of the reaction vessel reached 80 ° C, a solution of 15.13 g (0.21 mol) of acrylic acid dissolved in 50 ml of DMF was added dropwise over 30 minutes. This temperature was maintained to carry out a reaction for 1 hour. An aromatic bischloromethyl compound in which a reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and α,α'-dichloro-p-xylene is dissolved in 500 ml of DMF in 30 minutes (implementation) A solution of 62.76 g of 2CM-Xy-BPFZ of Example 2 was added dropwise. After the completion of the dropwise addition, stirring was continued at 80 ° C for 3 hours. After 3 h, cooled to room temperature and filtered to precipitate solids. Things. Then, 2000 ml of toluene was added to the reaction solution. Thereafter, the reaction solution was washed with water four times, and the oil phase was dried with magnesium sulfate and filtered. With respect to the obtained organic phase, the product was reprecipitated by a water/methanol mixed solvent.

The precipitate was filtered and dried to obtain 54.3 g of 2A-Xy-BPFZ as a reaction product of 2CM-Xy-BPFZ and acrylic acid.

The product was confirmed by gel permeation chromatography (GPC), infrared spectroscopy (IR), and ¹ H nuclear magnetic resonance spectroscopy ( ¹ H-NMR), and it was confirmed from GPC that the reaction was recovered. The peak from the raw material disappeared, and a new peak was formed on the high molecular weight side. From the IR, it was confirmed that a carbonyl group was formed, and in ¹ H-NMR, a resonance ray having a proton derived from an acrylic group was confirmed. Therefore, it was confirmed that 2A-Xy-BPFZ was obtained.

Example 8

8 g of 2A-DMBP-BPFZ obtained in Example 6 and o-phenyl-phenoxyethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester A-LEN-10) 12 g as a reactive diluent And 0.40 g of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184) as a photopolymerization initiator was mixed and dissolved to obtain a curable composition (varnish C).

A cured plate was prepared using the prepared varnish C by the same procedure as in Example 5, and the properties were measured. Further, a flat plate cured product having a thickness of 0.2 mm was cut into 0.3 cm × 10 cm to prepare a test piece, and a dielectric constant and a dielectric tangent of 2.0 GHz were measured. These tests The results obtained are shown in Table 2.

Example 9

8 g of 2A-Xy-BPFZ obtained in Example 7 and o-phenyl-phenoxyethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester A-LEN-10) 12 g as a reactive diluent And 0.40 g of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184) as a photopolymerization initiator was mixed and dissolved to obtain a curable composition (varnish D).

A cured plate was prepared using the prepared varnish D by the same procedure as in Example 5, and the properties were measured. Further, a flat plate cured product having a thickness of 0.2 mm was cut into 0.3 cm × 10 cm to prepare a test piece, and a dielectric constant and a dielectric tangent of 2.0 GHz were measured. The results obtained by these measurements are shown in Table 2.

Example 10

2MA-DMBP-BPFZ 11 g obtained in Example 3 and divinylbenzene (manufactured by Nippon Steel Chemical Co., Ltd., trade name: DVB960) 2 g, 9, 9-bis [4-( 2-propenyloxyethoxy)phenyl]anthracene (manufactured by Osaka Gas Chemicals Co., Ltd., trade name: Ogsol EA-0200) 1 g, phenyl thioethyl acrylate (BIMAX company, trade name: BX-PTEA 6 g of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184) as a photopolymerization initiator 0.40 g and a tertiary butylperoxy-2-ethyl hexanoate ( Nippon Oil Co., Ltd. Product Name: Perbutyl O) 0.04 g was mixed and dissolved to obtain a hardenable composition (varnish E).

A cured plate was prepared using the prepared varnish E by the same procedure as in Example 5, and the properties were measured. Further, a flat plate cured product having a thickness of 0.2 mm was cut into 0.3 cm × 10 cm to prepare a test piece, and a dielectric constant and a dielectric tangent of 2.0 GHz were measured. The results obtained by these measurements are shown in Table 3.

Example 11

2MA-Xy-BPFZ 11g obtained in Example 4 and divinylbenzene (manufactured by Nippon Steel Chemical Co., Ltd., trade name: DVB960) as a reactive diluent 2g, 9,9-bis [4-( 2-propenyloxyethoxy)phenyl]anthracene (manufactured by Osaka Gas Chemicals Co., Ltd., trade name: Ogsol EA-0200) 1 g, phenyl thioethyl acrylate (BIMAX company, trade name: BX-PTEA 6 g of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184) as a photopolymerization initiator 0.40 g and a tertiary butylperoxy-2-ethyl hexanoate ( Nippon Oil Co., Ltd., trade name: Perbutyl O) 0.04 g was mixed and dissolved to obtain a curable composition (varnish F).

A cured plate was prepared using the prepared varnish F by the same procedure as in Example 5, and the properties were measured. Further, a flat plate cured product having a thickness of 0.2 mm was cut into 0.3 cm × 10 cm to prepare a test piece, and a dielectric constant and a dielectric tangent of 2.0 GHz were measured. These tests The results obtained are shown in Table 3.

Claims (10)

A bis(methyl)acrylonitrile-terminated benzyl ether compound characterized by the following formula (2), (wherein Ar ¹ represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, Y represents hydrogen or a methyl group, n represents a number of 1 to 10, and R ¹ and R ² independently represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms or An aromatic hydrocarbon group having 6 to 12 carbon atoms; p and q independently represent an integer of 0 to 2). A process for producing a benzyl ether compound having a bis(meth)acrylonyl end group according to the first aspect of the invention, characterized in that the aromatic dihalomethyl compound represented by the following formula (1) is a (meth)acrylic compound represented by the formula (4), (wherein Ar ¹ represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, X represents a halogen element, n represents a number of 1 to 10, and R ¹ and R ² independently represent an aliphatic hydrocarbon group or a carbon number of 1 to 12 carbon atoms. 6 to 12 aromatic hydrocarbon groups; p and q independently represent an integer of 0 to 2), (wherein Y represents hydrogen or a methyl group, and Z represents hydrogen, an alkali metal, or a (meth)acrylonitrile group). A curable resin composition comprising a benzyl ether compound having a bis(meth)acryl fluorenyl terminal as in the first aspect of the patent application and a polymerization initiator. A curable film obtained by forming a curable resin composition according to item 3 of the patent application form into a film. A film obtained by hardening a curable film as disclosed in claim 4 of the patent application. A cured product obtained by hardening a curable resin composition as in item 3 of the patent application. A curable composite material comprising a curable resin composition according to item 3 of the patent application and a substrate. A hardened composite material characterized by hardening a hardenable composite material according to item 7 of the patent application. An optical article made of a cured product as in claim 6 of the patent application. An optical article as claimed in claim 9 wherein the optical object The product is an optical lens.