JP5195107B2 - Imide skeleton resin, curable resin composition, and cured product thereof - Google Patents

Description

  The present invention relates to a resin containing an imide skeleton structure as an essential component, a curable resin composition containing the resin, a cured product thereof, and a laminate including the cured product.

  The imide skeleton resin of the present invention can provide a curable resin composition suitable as a constituent material of an electrical laminate such as a printed wiring board having a high glass transition temperature and a low thermal expansion coefficient. Here, the electric laminate refers to a laminate used for an insulating substrate including a printed wiring board, a build-up laminate, a flexible laminate, a resist material, a sealant, and the like.

  Epoxy resins are excellent in heat resistance, adhesion, water resistance, mechanical strength, electrical properties, etc., so they are used in various fields such as adhesives, paints, materials for civil engineering and construction, and insulation materials for electrical and electronic parts. It is used. In particular, in the electric / electronic field, it is widely used in insulating casting, laminated materials, sealing materials and the like.

In recent years, printed wiring boards used in electrical and electronic equipment are becoming smaller, lighter, and more functional, especially with respect to multilayer printed wiring boards. There are demands for reduction in weight and weight, and improvement in reliability and moldability.
Thus, as the miniaturization of wiring progresses, further improvements in heat resistance and low linear expansion coefficient are particularly required as characteristics toward the resin side as a substrate material.

  At present, polyimide resin is used as the thermosetting resin made of low linear expansion, and it has become mainstream in the field of flexible printed wiring boards. However, the polyimide resin is difficult to be molded because of its high heat resistance, and is difficult to handle during processing because it is soluble only in a special polar solvent, and is subject to various restrictions.

On the other hand, the epoxy resin is superior in molding processability to the polyimide resin, but the linear expansion coefficient is not sufficiently satisfactory.
Conventionally, epoxy resins having a low coefficient of linear expansion include anthracene skeleton epoxy resin, bisphenol S skeleton epoxy resin, and naphthalene skeleton epoxy resin, but the coefficient of linear expansion is not as high as that of polyimide resin.

Japanese Patent Application Laid-Open No. 2006-83128 describes an epoxy resin having an imide skeleton and is described as being useful as a raw material monomer for a polymer material such as a phenol / epoxy resin. There is no description about the prescription.
JP 2006-83128 A

  When the conventional epoxy resin is used for the resin composition for electrical laminates, a low linear expansion coefficient comparable to that of a polyimide resin cannot be achieved. On the other hand, a polyimide resin does not have sufficient moldability.

Accordingly, an object of the present invention is to provide an imide skeleton resin having a low linear expansion coefficient comparable to that of a polyimide resin, excellent in moldability like an epoxy resin, and useful for a resin composition for an electrical laminate. To do.
Another object of the present invention is to provide a curable resin composition containing the imide skeleton resin, a cured product thereof, and a laminate including the cured product.

  The present invention includes the following inventions.

[1] An imide skeleton resin represented by the following general formula (1).

(In the formula, A is a linking group represented by the following general formula (2-1), the following general formula (3-1), or the following general formula (4-1), and n + 1 A's are the same as each other. However, 5 mol% or more in all the components A is a linking group represented by the following general formula (4-1).
B is Ru Oh a group represented by the Symbol structural formula (5).
n is an integer of 0-200 . )

(Wherein R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₁ may be the same as or different from each other. Two R ₁ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.
m is 0 or 1.
X is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —SO ₂ —, or CO—. )

(Wherein R ₂ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₂ may be the same as or different from each other. Two R ₂ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.

(Wherein R ₃ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₃ may be the same as or different from each other. Two R ₃ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.
R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a phenyl group, or a hydrocarbon group having 1 to 10 carbon atoms. )

[2] The imide skeleton resin according to [1], wherein the linking group represented by the general formula (4-1) is represented by the following general formula (6-1).

(Wherein R ₇ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₇ may be the same as or different from each other. Two R ₇ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.

[3] In [1] or [2], the epoxy equivalent is 250 g / eq. An imide skeleton resin characterized by the above.

[4] In any one of [1] to [3], the cured product obtained by blending only the curing agent and the curing accelerator has a glass transition temperature of 100 ° C. or higher and a linear expansion coefficient of 75 ppm / below the glass transition temperature. Imide skeleton resin characterized by being less than ° C.

[5] A divalent phenol compound represented by any one of the following general formula (2-2), the following general formula (3-2), and the following general formula (4-2), and an epihalohydrin are present in the presence of an alkali. The method for producing an imide skeleton resin according to any one of [1] to [4], wherein the reaction is performed under the following conditions.

（式中、Ｒ_１、Ｘ、ｍは、それぞれ前記一般式（２−１）におけると同義である。）

(In the formula, R ₁ , X, and m are respectively synonymous with those in the general formula (2-1).)

（式中、Ｒ_２は、前記一般式（３−１）におけると同義である。）

(In the formula, R ₂ has the same meaning as in the general formula (3-1).)

（式中、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６は、それぞれ前記一般式（４−１）におけると同義である。）

(In formula, R < ₃ >, R < ₄ >, R < ₅ >, R < ₆ > is respectively synonymous with the said general formula (4-1).)

[6] A bifunctional epoxy resin represented by any one of the following general formula (7), the following general formula (8), and the following general formula (9), the following general formula (2-2), and the following general formula ( Any one of [1] to [4], wherein 3-2) and a dihydric phenol compound represented by any one of the following general formula (4-2) are reacted in the presence of a catalyst The manufacturing method of imide frame | skeleton resin as described in 2 ..

（式中、Ｒ_１、Ｘは、それぞれ前記一般式（２−１）におけると同義である。lは０または１であり、ｐは０〜１０の整数である。）

(Wherein R ₁ and X have the same meanings as in the general formula (2-1), l is 0 or 1, and p is an integer of 0 to 10)

（式中、Ｒ_２は前記一般式（３−１）におけると同義である。ｑは０〜１０の整数である。）

(In the formula, R ₂ has the same meaning as in formula (3-1). Q is an integer of 0 to 10.)

（式中、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６は、それぞれ前記一般式（４−１）におけると同義である。ｒは０〜１０の整数である。）

_{(Wherein, R 3, R 4, R} 5, R 6 , the .r synonymous as in each of the general formula (4-1) is an integer of 0.)

（式中、Ｒ_１、Ｘ、ｍは、それぞれ前記一般式（２−１）におけると同義である。）

(In the formula, R ₁ , X, and m are respectively synonymous with those in the general formula (2-1).)

（式中、Ｒ_２は、前記一般式（３−１）におけると同義である。）

(In the formula, R ₂ has the same meaning as in the general formula (3-1).)

（式中、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６は、それぞれ前記一般式（４−１）におけると同義である。）

(In formula, R < ₃ >, R < ₄ >, R < ₅ >, R < ₆ > is respectively synonymous with the said general formula (4-1).)

[7] A curable resin composition comprising the imide skeleton resin according to any one of [1] to [4].

[8] The curable resin composition according to [7], further comprising a curing agent and a curing accelerator.

[9] In [7] or [8], it further includes one or more selected from the group consisting of epoxy resins other than the imide skeleton resin, thermosetting resins other than epoxy resins, and inorganic fillers. A curable resin composition characterized by that.

[10] The curable resin composition according to any one of [7] to [9], which is used for a printed wiring board.

[11] A cured resin product obtained by curing the curable resin composition according to any one of [7] to [10].

[12] A laminate of the cured resin according to [11] and a conductive metal.

The imide skeleton resin of the present invention and the curable resin composition containing the imide skeleton resin have a low coefficient of linear expansion, excellent heat resistance (glass transition temperature) and molding processability, and are particularly required to have a low coefficient of linear expansion. Useful in applications.
ADVANTAGE OF THE INVENTION According to this invention, the resin hardened | cured material and laminated body useful for an electrical laminated board, especially a printed wiring board are provided.

  Hereinafter, embodiments of the present invention will be described in detail.

[Imide skeleton resin]
The imide skeleton resin of the present invention is represented by the following general formula (1).

(In the formula, A is a linking group represented by the following general formula (2-1), the following general formula (3-1), or the following general formula (4-1), and n + 1 A's are the same as each other. However, 5 mol% or more in all the components A is a linking group represented by the following general formula (4-1).
B is a hydrogen atom or a group represented by the following structural formula (5), and the two Bs may be the same as or different from each other.
n is an integer of 0-200.
However, when both B are hydrogen atoms, n is an integer of 1 or more. )

(Wherein R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₁ may be the same as or different from each other. Two R ₁ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.
m is 0 or 1.
X is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —SO ₂ —, or CO—. )

(Wherein R ₂ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₂ may be the same as or different from each other. Two R ₂ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.

(Wherein R ₃ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₃ may be the same as or different from each other. Two R ₃ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.
R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a phenyl group, or a hydrocarbon group having 1 to 10 carbon atoms. )

<A component>
A in General Formula (1) is a linking group represented by General Formula (2-1), General Formula (3-1), or General Formula (4-1). In -1), R ₁ is preferably a hydrogen atom or a methyl group, and X is preferably a single bond or a methylene group or a propylene group optionally substituted with an alkyl group having 1 to 6 carbon atoms.
In General Formula (3-1), R ₂ is preferably a hydrogen atom, a methyl group, or a cyclic group having 4 carbon atoms bonded to an adjacent carbon atom on the naphthalene ring.
In the general formula (4-1), R ₃ is preferably a hydrogen atom or a methyl group.
R ₄ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, and R ₅ and R ₆ are preferably a hydrogen atom or a methyl group.

In particular, the linking group represented by the general formula (4-1) is preferably represented by the following general formula (6-1), in which R ₇ is preferably a hydrogen atom or a methyl group, and the bond The hand position is preferably a meta position and / or a para position with respect to a position where the imide group of the benzene ring is bonded.
The linking group represented by the general formula (6-1) is particularly preferably a linking group represented by the following structural formula (10-1).

(Wherein R ₇ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₇ may be the same as or different from each other. Two R ₇ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.

<Mole content of imide skeleton in A>
The component A of the imide skeleton resin of the present invention represented by the general formula (1) is represented by the general formula (2-1), the general formula (3-1), or the general formula (4-1). Although it is a linking group, the ratio of the linking group represented by the general formula (4-1) in all the components A in the general formula (1) (hereinafter, this ratio is referred to as “molar content of imide skeleton in A”). In some cases) is 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more.

When the molar content of the imide skeleton in A is less than 5 mol%, the linear expansion coefficient and the heat resistance become insufficient.
In addition, the upper limit of imide skeleton molar content in A is 100 mol%.

<B component>
B in the general formula (1) is a hydrogen atom or a group represented by the following structural formula (5), and the two Bs may be the same or different.

  In the general formula (1), the ratio of the group represented by the structural formula (5) in the total B component is not particularly limited, and may be larger or smaller than the ratio of hydrogen atoms. All the B components may be groups represented by the following structural formula (5), or all may be hydrogen atoms.

  The ratio of the group represented by the following structural formula (5) in all B components may be, for example, 10 to 100 mol%, preferably 20 to 100 mol%, and the ratio of hydrogen atoms in all B components However, it may be, for example, 10 to 100 mol%, preferably 20 to 100 mol%.

<Value of n / number average molecular weight>
The number average molecular weight of the imide skeleton resin of the present invention is usually 500 or more, more preferably 550 or more. However, when the number average molecular weight exceeds 120,000, the resin becomes extremely viscous and handling of the resin becomes difficult. It is not preferable. From the viewpoint of both heat resistance and resin handling properties, the number average amount of the imide skeleton resin of the present invention is preferably 100,000 or less, more preferably 80,000 or less.

Such an imide skeleton resin having a number average molecular weight is usually 0 to 200 as the value of n in the general formula (1).
In the imide skeleton resin of the present invention, in the general formula (1), when both B are hydrogen atoms, n is 1 or more.

  The number average molecular weight of the imide skeleton resin of the present invention is adjusted by adjusting the molar ratio of epihalohydrin and dihydric phenol compound or the molar ratio of bifunctional epoxy resin and dihydric phenol compound in the method for producing imide skeleton resin described later. By doing so, it can be produced as an imide skeleton resin having a target value.

  In addition, the number average molecular weight of imide skeleton resin, the value of n, and the average value can be calculated | required by the method described in the term of the below-mentioned Example.

<Epoxy equivalent>
The epoxy equivalent of the imide skeleton resin of the present invention is 250 g / eq. The above is preferable. The upper limit of the epoxy equivalent is not particularly limited, but is usually 100,000 g / eq. It is as follows.

<Amount of saponifiable chlorine>
The imide skeleton resin of the present invention preferably has a small amount of saponifiable chlorine which is an end group impurity of the epoxy resin, and the amount of saponifiable chlorine is preferably 900 ppm or less, and preferably 700 ppm or less. If the amount of saponifiable chlorine is high, for example, it exceeds 1000 ppm, it causes deterioration of electrical characteristics, which is not preferable. Although the saponifiable chlorine content is preferably as low as possible, it is usually 10 ppm or more for industrial products. However, when it is lower than that, for example, it may be 2 to 4 ppm.

<Glass transition temperature and linear expansion coefficient of specific cured products>
The imide skeleton resin of the present invention is a glass transition of a cured product obtained by blending only a curing agent and a curing accelerator in the imide skeleton resin (hereinafter, this cured product may be referred to as “specific cured product”). The linear expansion coefficient (CTE) at a temperature (Tg) of 100 ° C. or higher and a glass transition temperature or lower is preferably less than 75 ppm / ° C.

  The specific cured product in which the glass transition temperature and the linear expansion coefficient are specified is specifically manufactured as follows according to the epoxy equivalent of the imide skeleton resin.

Curing Method I: (In the case of an imide skeleton resin having an epoxy equivalent of 5000 g / eq. Or more)
100 g of solid content of imide skeleton resin, 1 g of curing agent: jER Cure YLH129 (Japan Epoxy Resin Co., Ltd. trade name, bisphenol A novolac resin, hydroxyl group equivalent 117 (g / eq.), Softening point 115 (° C.)), Curing accelerator: 0.5 g of 2-ethyl-4-methylimidazole, 80 g of cyclohexane and 80 g of dimethylacetamide were mixed in a 1000 ml beaker, and a Teflon film (Nichias Co., Ltd.) using an applicator with a slit width of 300 μm. : Teflon tape TOMBO9001), a coating film was drawn on a hot air dryer at 170 ° C. for 30 minutes and further held at 200 ° C. for 90 minutes to obtain a specific cured product having a thickness of 60 to 100 μm.

Curing method II: (In the case of an imide skeleton resin having an epoxy equivalent of less than 5000 g / eq.)
100 g of solid content of imide skeleton resin and curing agent: jER Cure YLH129 (trade name of Japan Epoxy Resin Co., Ltd., bisphenol A novolac resin, hydroxyl group equivalent 117 (g / eq.), Softening point 115 (° C.)) [(100 × 117) ÷ (Epoxy equivalent of imide skeleton resin)] g and curing accelerator: 0.3 g of 2-ethyl-4-methylimidazole was charged into a 200 ml beaker, heated on a hot plate at 260 ° C., melt mixed, After defoaming the melt-mixed resin under reduced pressure, it was heated at 170 ° C. for 30 minutes and then heated at 200 ° C. for 90 minutes in a safe ben dryer to obtain a specific cured product.

  The glass transition temperature and the linear expansion coefficient of the specific cured product thus obtained are measured by the methods shown in the Examples section below.

  If the glass transition temperature is less than 100 ° C., the high heat resistant resin intended in the present invention cannot be obtained. This glass transition temperature is preferably 130 ° C. or higher, more preferably 140 ° C. or higher. The higher the glass transition temperature, the better, but it is usually 250 ° C. or lower.

In addition, when the linear expansion coefficient is 75 ppm / ° C. or more, a resin having a low linear expansion coefficient intended in the present invention cannot be obtained. The linear expansion coefficient is preferably as low as possible, more preferably 70 ppm / ° C. or more, and still more preferably 65 ppm / ° C. or less.
The lower the linear expansion coefficient, the better, but it is usually 50 ppm / ° C. or higher.

[Method for producing imide skeleton resin]
Although there is no restriction | limiting in particular as a manufacturing method of imide frame | skeleton resin of this invention, It can manufacture by the following one-stage methods or two-stage methods.

<One-step method>
A dihydric phenol compound represented by any one of the following general formula (2-2), the following general formula (3-2), and the following general formula (4-2); and an epihalohydrin such as epichlorohydrin or epibromohydrin; In the presence of alkali.

（式中、Ｒ_１、Ｘ、ｍは、それぞれ前記一般式（２−１）におけると同義である。）

(In the formula, R ₁ , X, and m are respectively synonymous with those in the general formula (2-1).)

（式中、Ｒ_２は、前記一般式（３−１）におけると同義である。）

(In the formula, R ₂ has the same meaning as in the general formula (3-1).)

（式中、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６は、それぞれ前記一般式（４−１）におけると同義である。）

(In formula, R < ₃ >, R < ₄ >, R < ₅ >, R < ₆ > is respectively synonymous with the said general formula (4-1).)

<Two-stage method>
A bifunctional epoxy resin represented by any one of the following general formula (7), the following general formula (8), and the following general formula (9), the above general formula (2-2), and the above general formula (3-2) And a dihydric phenol compound represented by any one of the above general formula (4-2) in the presence of a catalyst.

（式中、Ｒ_１、Ｘは、それぞれ前記一般式（２−１）におけると同義である。lは０または１であり、ｐは０〜１０の整数である。）

(Wherein R ₁ and X have the same meanings as in the general formula (2-1), l is 0 or 1, and p is an integer of 0 to 10)

（式中、Ｒ_２は前記一般式（３−１）におけると同義である。ｑは０〜１０の整数である。）

(In the formula, R ₂ has the same meaning as in formula (3-1). Q is an integer of 0 to 10.)

（式中、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６は、それぞれ前記一般式（４−１）におけると同義である。ｒは０〜１０の整数である。）

_{(Wherein, R 3, R 4, R} 5, R 6 , the .r synonymous as in each of the general formula (4-1) is an integer of 0.)

  The dihydric phenol compound used in the production of the one-step method and the two-step method is represented by the general formula (2-2), the general formula (3-2), and the general formula (4-2). In the present invention, one kind of these may be used alone, or two or more kinds may be mixed and used. Moreover, unless the objective of this invention is impaired, you may use together the bivalent phenolic compound which has two hydroxyl groups couple | bonded with the aromatic ring in a molecule | numerator other than these bivalent phenolic compounds.

  Examples of the dihydric phenol compound represented by the general formula (2-2) include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol acetophenone, bisphenol fluorenone, bisphenol B, bisphenol AD, and 4,4 ′. -Biphenols such as biphenol, 3,3 ', 5,5'-tetramethyl-4,4'-biphenol, catechol, resorcin, hydroquinone, etc. are mentioned, in particular bisphenol A, bisphenol F, 4,4'- Biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, bisphenol acetophenone and bisphenol fluorenone are preferred.

  Examples of the divalent phenol compound represented by the general formula (3-2) include dihydroxynaphthalene, dihydroxyanthracene, and dihydroxydihydroanthracene, and dihydroxynaphthalene and dihydroxydihydroanthracene are particularly preferable.

  As the divalent phenol compound represented by the general formula (4-2), a compound represented by the following general formula (6-2) is more preferable, and particularly a compound represented by the following structural formula (10-2). Is preferred.

（式中、Ｒ_７は、前記一般式（６−１）におけると同義である。）

(Wherein R ₇ has the same meaning as in formula (6-1)).

  The bifunctional epoxy resin used in the production of the two-stage method is an epoxy resin represented by the general formula (7), the general formula (8), and the general formula (9). These 1 type may be used independently and may mix and use 2 or more types. Moreover, unless the objective of this invention is impaired, you may use together the bifunctional epoxy compound which has two epoxy groups in a molecule | numerator other than these bifunctional epoxy resins.

  Examples of the bifunctional epoxy resin represented by the general formula (7) include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, and bisphenol acetophenone. Type epoxy resin, bisphenol fluorenone type epoxy resin, diglycidyl ether of monocyclic dihydric phenol such as catechol, resorcin, hydroquinone and the like. Particularly preferred among these epoxy resins are bisphenol A type epoxy resins, bisphenol F type epoxy resins, 4,4′-biphenol type epoxy resins, 3,3 ′, 5,5′-tetramethyl-4,4. '-Biphenol type epoxy resin.

  Examples of the bifunctional epoxy resin represented by the general formula (8) include dihydroxynaphthalene type epoxy resins and dihydroxy dihydroanthracene type epoxy resins.

  Examples of the bifunctional epoxy resin represented by the general formula (9) include imide skeleton type epoxy resins.

  Examples of the bifunctional epoxy compound that may be used in combination other than the bifunctional epoxy resin represented by the general formulas (7), (8), and (9) include an alicyclic epoxy resin, a diglycidyl ether of a dihydric alcohol, And diglycidyl esters of divalent carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid and hexahydrophthalic acid. These epoxy compounds may be substituted with a substituent having no adverse effect such as an alkyl group, an aryl group, an ether group or an ester group. These epoxy compounds can be used in combination of a plurality of types, but the amount used is preferably 30% by weight or less in the total bifunctional epoxy resin (compound).

  The raw material compound is used in a predetermined ratio so that an imide skeleton resin having a target chemical structure, an imide skeleton molar content in A, and a number average molecular weight can be obtained.

  As the alkali that can be used in the one-step method, one or more of sodium hydroxide, potassium hydroxide, and the like can be used. The ratio is about 0.2 to 2.0.

  On the other hand, the catalyst used in the two-stage method may be any compound as long as it has a catalytic ability to promote the reaction between an epoxy group and a phenolic hydroxyl group. For example, an alkali metal compound, an organic phosphorus compound, etc. , Tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like. An organic phosphorus compound and a quaternary ammonium salt are preferable.

  Specific examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide; alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride; sodium Examples include alkali metal alkoxides such as methoxide and sodium ethoxide; alkali metal phenoxides, sodium hydride, lithium hydride and the like; and alkali metal salts of organic acids such as sodium acetate and sodium stearate.

  Specific examples of the organic phosphorus compound include tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, Trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, Triphenylethylphosphonium iodai , Triphenyl benzyl phosphonium chloride, triphenyl benzyl phosphonium bromide and the like.

  Specific examples of the tertiary amine include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine and the like.

  Specific examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, Tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride Id, and a phenyl trimethyl ammonium chloride.

  Specific examples of cyclic amines include 1,8-diazabicyclo (5,4,0) undecene-7,1,5-diazabicyclo (4,3,0) nonene-5.

  Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.

  These catalysts may be used alone or in combination of two or more.

  The amount of these catalysts used is preferably 0.001 to 1% by weight based on the reaction solid content.

  In both the one-step method and the two-step method, a solvent may be used in the step of the synthesis reaction during the production, and any solvent can be used as long as it dissolves the imide skeleton resin and does not adversely affect the reaction. It may be anything. Examples thereof include aromatic hydrocarbons, alcohols, ketones, amide solvents, glycol ethers and the like. Alcohols, ketones, and amide solvents are preferable.

Specific examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like.
Examples of alcohols include methanol, ethanol, propanol, butanol and the like.
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, and dioxane.
Specific examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like.
Specific examples of glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono -N-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate and the like.

  These solvents may be used alone or in combination of two or more.

  The amount of the solvent to be used can be appropriately selected depending on the reaction conditions. For example, in the case of the two-stage production, it is preferable that the solid concentration is 35 to 95% by weight. In the case of time, it is preferable to use about 0.2-2.0 by molar ratio with respect to epihalohydrin. Further, when a highly viscous product is produced during the reaction, the reaction can be continued by adding a solvent during the reaction. After completion of the reaction, the solvent can be removed by distillation or the like, if necessary, or further added.

The reaction temperature during the one-step production of the imide skeleton resin of the present invention is in the temperature range of about 40 to 130 ° C. The reaction temperature is preferably 40 to 80 ° C, more preferably 45 to 70 ° C.
The reaction time is usually about 30 to 240 minutes.

The reaction temperature during the two-step production of the imide skeleton resin of the present invention is within a temperature range in which the catalyst used does not decompose. The reaction temperature is preferably 50 to 230 ° C, more preferably 120 to 200 ° C. When using a low boiling point solvent such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by carrying out the reaction under high pressure using an autoclave.
The reaction time is usually about 1 to 12 hours.

[Curable resin composition]
The curable resin composition of the present invention contains the imide skeleton resin of the present invention. In addition to the imide skeleton resin of the present invention, the curable resin composition of the present invention further includes an epoxy resin other than the imide skeleton resin, a curing agent, a curing accelerator, a thermosetting resin other than the epoxy resin, a solvent, and an inorganic filling. An agent, a fiber base material, and other various additive components can be included.

<Epoxy resin other than imide skeleton resin>
There is no restriction | limiting in particular as epoxy resins other than the imide frame | skeleton resin which the curable resin composition of this invention can contain, For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin , Phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolak type epoxy resins, epoxy resins obtained by reacting phenols with aldehydes such as glyoxal, hydroxybenzaldehyde and crotonaldehyde, and epihalohydrin Glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin It includes various epoxy resins and the like. These may be used alone or in combination of two or more.

  When the curable resin composition of the present invention contains an epoxy resin other than the imide skeleton resin of the present invention, the content varies depending on the use of the curable resin composition, the characteristics required for the curable resin composition, and the like. However, it is usually preferable to use 40 parts by weight or less, for example, 20 to 30 parts by weight in 100 parts by weight of the total epoxy resin (total of imide skeleton resin and epoxy resin other than imide skeleton resin). By blending an epoxy resin other than the imide skeleton resin of the present invention, there is an effect of improving flexibility and compatibility. However, if the blending amount is too large, the heat resistance by the imide skeleton resin of the present invention and The effect of low linear expansion, particularly low linear expansion, may be impaired.

<Curing agent>
As the curing agent for the imide skeleton resin, when the terminal group of the imide skeleton resin is an epoxy group, a general curing agent for epoxy resin is used. For example, aromatic polyamines, dicyandiamide, acid anhydrides, various phenols A novolak resin etc. are mentioned. These may be used alone or in combination of two or more.
In addition, when the terminal group of the imide skeleton resin is an OH group, it is preferable to use an epoxy resin as a cured product, such as a phenol novolac type epoxy resin, a cresol volac type epoxy resin, a bisphenol A volac type epoxy resin, etc. Is mentioned. These may be used alone or in combination of two or more.

  The content of the curing agent in the curable resin composition varies depending on the type of the curing agent used, but is usually 0.5 to 100 parts by weight, preferably 1 to 95 parts by weight with respect to 100 parts by weight of the total epoxy resin. Is within the range.

<Curing accelerator>
As the curing accelerator, any of those used in general epoxy resin compositions can be used, for example, amines such as benzyldimethylamine and various imidazole compounds, tertiary phosphines such as triphenylphosphine, etc. Is mentioned. These may be used alone or in combination of two or more.

  The curing accelerator is preferably blended in an amount of 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the total epoxy resin.

<Thermosetting resin other than epoxy resin>
Examples of thermosetting resins other than epoxy resins include cyanate ester resins, thermosetting polyimide resins, thermosetting polyphenylene ether resins, and the like. These may be used alone or in combination of two or more.

  When the curable resin composition of this invention contains these thermosetting resins, it is preferable that the content shall be 40 weight part or less with respect to 100 weight part of all the epoxy resins, for example, 10-30 weight part. When the curable resin composition contains a thermosetting resin other than the epoxy resin, the water absorption can be reduced. However, when the content is too large, the effect of using the imide skeleton resin of the present invention, May damage the properties of the epoxy resin.

<Solvent>
Examples of the solvent that can be contained in the curable resin composition of the present invention include ketones such as acetone, methyl ethyl ketone, toluene, xylene, and methyl isobutyl ketone, esters such as ethyl acetate, ethers such as ethylene glycol monomethyl ether, N, Examples thereof include amides such as N-dimethylformamide and N, N-dimethylacetamide, and alcohols such as methanol and ethanol.
These solvents may be used alone or in combination of two or more.

  The amount of the solvent used is appropriately determined according to the purpose of use of the curable resin composition. For example, when a prepreg is prepared by impregnating a glass fiber nonwoven fabric with a curable resin composition in a laminate application, a solvent other than the solvent is used. It is used so that the total solid content concentration in the curable resin composition is about 40 to 70% by weight. In build-up applications, the total solid content concentration in the curable resin composition other than the solvent is 35 to 35%. It is used so that it may become about 75 weight%.

<Inorganic filler>
Examples of inorganic fillers include metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as finely divided silica, fused silica and crystalline silica, transparent fillers such as glass beads, and metal hydroxides such as aluminum hydroxide and magnesium hydroxide. And other materials such as calcium carbonate, kaolin, mica, quartz powder, graphite, molybdenum disulfide, and the like. These may be used alone or in combination of two or more.

  The inorganic filler has a mean particle size of about 1 to 30 μm because the surface shape of the cured product is deteriorated if the particle size is too large, and if the particle size is too small, it tends to aggregate and deteriorate dispersibility. .

  When the curable resin composition of this invention contains these inorganic fillers, it is preferable that the content shall be 80 weight part or less with respect to 100 weight part of all the epoxy resins, for example, 10-60 weight part. When the curable resin composition contains an inorganic filler, effects of improving flame retardancy, improving low water absorption, and reducing linear expansion coefficient can be obtained. However, if the content is too large, moldability and the like are impaired. There is a fear.

<Resin substrate>
Examples of the fiber substrate include inorganic fiber cloth such as glass fiber cloth, glass fiber nonwoven fabric, and organic fiber nonwoven fabric. These may be used alone or in combination of two or more.

  The curable resin composition containing these fiber base materials can be formed by various techniques such as application and impregnation of the curable resin composition on the fiber base material, and various fibers can be used depending on the method. The substrate content can be set.

<Other ingredients>
The curable resin composition of the present invention includes other anti-UV agents for improving storage stability, plasticizers, silane coupling agents, coupling agents such as titanate coupling agents, colorants and pigments, flame retardancy Various additives that can be blended in a normal epoxy resin composition, such as a halogen-based, phosphorus-based, nitrogen-based, silicon-based flame retardant, glass fiber reinforcing agent, etc. It can mix | blend in the range which does not impair the objective.

  The curable resin composition of the present invention can be prepared by mixing predetermined amounts of the above-described blending components.

[Usage]
The curable resin composition containing the imide skeleton resin of the present invention can be effectively used in various fields such as adhesives, paints, materials for civil engineering and construction, insulating materials for electric / electronic parts, etc. Because of its excellent heat resistance, low linear expansion, and moldability, it is suitably used for multilayer electric laminates and new-type printed wiring boards such as build-up methods. In particular, use in the form of a resin-coated copper foil, an adhesive film, or the like used as a build-up method multilayer printed wiring board material is preferable. It can also be used for flexible laminate applications, resist materials, sealing materials and the like.
The imide skeleton resin of the present invention can be used after being modified with acrylic acid, methacrylic acid or the like.

As shown in FIG. 1, the build-up method is a film (insulating layer) having a thickness of 40 to 90 μm on an inner circuit board (core substrate, 1A indicates a circuit) 1 in which glass prepregs are laminated, or a film. 2 is a method of laminating a film 3 with a copper foil on which a copper foil 2A (copper foil thickness: 9 to 18 μm) is laminated, and in general, this laminating press step, drilling (laser or drill) step The circuit is formed through two types of desmear / plating processes. The build-up method is an excellent method for reducing the size and weight, because the obtained laminated plate has the same performance as a conventional laminated plate, and the mounting area and weight are about 1/4.
The curable resin composition containing the imide skeleton resin of the present invention is useful as a film with a copper foil or a resin material for a film used in this build-up method.

[Resin cured product]
The cured resin product of the present invention is obtained by curing the curable resin composition of the present invention.
Although the hardening method of the curable resin composition of this invention changes also with the compounding component and compounding quantity in curable resin composition, the heating conditions for 60 to 180 minutes are normally mentioned at 100-200 degreeC. This heating may be performed by a two-stage treatment of primary heating at 100 to 130 ° C. for 10 to 30 minutes and secondary heating at 150 to 200 ° C. that is 50 to 80 ° C. higher than the primary heating temperature for 60 to 150 minutes, This is preferable from the viewpoint of reducing curing failure.

[Laminate]
The laminate of the present invention is a laminate of the cured resin of the present invention and a conductive metal obtained by curing the curable resin composition of the present invention. Preferably, the build-up used in the aforementioned build-up method is used. It is a film with a conductive metal foil as a layer.

  As the conductive metal foil of the film with the conductive metal foil, a metal foil such as copper or aluminum is used, and the thickness is usually about 9 to 19 μm. Moreover, as a film, the thing about 40-90 micrometers thick is used normally.

  As shown in the Examples section below, this laminate was prepared by using a solvent to prepare a coating solution in which the curable resin composition of the present invention was adjusted to an appropriate viscosity, and using this coating solution as a metal such as copper foil. It can be manufactured by applying to a foil and semi-curing by heating under the above-mentioned primary heating conditions. As shown in FIG. 1, the laminated body in which the resin side is semi-cured is laminated on the core substrate 1 and then completely cured by heating under the above-mentioned secondary heating conditions under a pressure of about 2 to 5 MPa. By integrating them, a printed wiring board can be obtained.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Example 1]
154 g of imide skeleton phenol compound represented by the above structural formula (10-2), 281 g of epichlorohydrin, and 148 g of 2-propanol are charged into a 2 L three-necked flask equipped with a thermometer, a stirrer, and a condenser. The solution was heated to 50 ° C. and dissolved, and 68 g of a 48.5% by weight aqueous sodium hydroxide solution was added dropwise over 1 hour. During this time, the temperature was gradually raised, and the temperature inside the system was adjusted to 70 ° C. at the end of dropping. Thereafter, the reaction was carried out by maintaining at 70 ° C. for 30 minutes. After completion of the reaction, the product was washed with water to remove by-product salts and excess sodium hydroxide. Subsequently, excess epichlorohydrin and 2-propanol were distilled off from the product under reduced pressure to obtain a crude epoxy resin.

  This crude epoxy resin was dissolved in 300 g of methyl isobutyl ketone, 5 g of 48.5 wt% aqueous sodium hydroxide solution was added, and the mixture was reacted at a temperature of 70 ° C. for 1 hour. After the reaction was completed, sodium phosphate monobasic was added to neutralize excess sodium hydroxide and washed with water to remove by-product salts. Next, methyl isobutyl ketone was completely removed under reduced pressure while heating to obtain the desired imide skeleton resin (I).

  The structure and physical properties of the imide skeleton resin (I) were examined by the following method, and the results are shown in Table 1.

<Chemical structure, molar content of imide skeleton in A>
It calculated from the raw material ratio. In addition, the value of n and the average value were computed from the number average molecular weight measured by the following method.

<Number average molecular weight>
TSK Standard Polystyrene: F-128 (Mw1,090,000, Mn1,030,000), F-10 (Mw106,000, Mn103,000), F-4 as standard polystyrene using an HLC-8120GPC apparatus manufactured by Tosoh Corporation (Mw43,000, Mn42,700), F-2 (Mw17,200, Mn16,900), A-5000 (Mw6,400, Mn6,100), A-2500 (Mw2,800, Mn2,700), A A calibration curve using -300 (Mw453, Mn387) was prepared, and the number average molecular weight was measured as a polystyrene equivalent value. Column: TSKGEL SuperHM-H + H5000 + H4000 + H3000 + H2000 manufactured by Tosoh Corporation. Eluent: THF. Flow rate: 0.6 ml / min. Detection: UV (254 nm). Temperature: 40 ° C. Sample concentration: 0.1%. Injection volume: 10 μl.

<Epoxy equivalent>
It was measured according to JIS K 7236 and expressed as a solid content converted value.

<Amount of saponifiable chlorine>
Measured according to JIS K 7242-2 and expressed as a solid content converted value.

<Glass transition temperature and linear expansion coefficient of specific cured product>
(Production of specific cured product)
A specific cured product was prepared by the following curing method II.
100 g of imide skeleton resin (I) and curing agent: jER cure YLH129 (trade name of Japan Epoxy Resin Co., Ltd., bisphenol A novolak resin, hydroxyl group equivalent 117 (g / eq.), Softening point 115 (° C.)) 39.4 g And a curing accelerator: 0.3 g of 2-ethyl-4-methylimidazole was charged into a 200 ml beaker, heated and melt-mixed on a hot plate at 260 ° C., and the melt-mixed resin was degassed under reduced pressure. Then, after heating at 170 ° C. for 30 minutes, it was heated at 200 ° C. for 90 minutes to obtain a specific cured product.
The glass transition temperature and average linear expansion coefficient of this specific cured product were examined by the following method, and the results are shown in Table 1.

<Glass transition temperature>
Using a 2010 DSC thermal analyzer manufactured by TA Instruments, 10 ° C./min. And the Tg was measured.

<Linear expansion coefficient>
Using a TMA / SS6100 device manufactured by SII Nanotechnology Co., Ltd., the temperature was increased from 20 to 250 ° C. at 5 ° C./min in a compression mode, and an average linear expansion coefficient from 30 ° C. to 130 ° C. was measured.

[Comparative Example 1]
A crude epoxy resin was obtained in the same manner as in Example 1 except that 188 g of bisphenol F, 385 g of epichlorohydrin, and 149 g of 2-propanol were charged as raw materials for a 2 L three-necked flask. 1 to obtain the desired epoxy resin (II).

  With respect to this epoxy resin (II), the structures and physical properties measured and evaluated in the same manner as in Example 1 are as shown in Table 1.

  Except that this epoxy resin (II) was used instead of the imide skeleton resin (I), a specific cured product was prepared in the same manner as in Example 1, and the glass transition temperature and the average linear expansion coefficient were similarly examined, The results are shown in Table 1.

[Examples 2 to 5, Comparative Example 2]
The compound (X), the compound (Y), the catalyst, and the solvent having the composition shown in Table 2 were placed in a pressure-resistant reaction vessel equipped with a stirrer, and reacted at 180 ° C. for 5 hours in a nitrogen gas atmosphere. After removing the solvent from the reaction product by a conventional method, the resulting resin was analyzed by the following method. The results are shown in Table 2.

<Number average molecular weight>
TSK Standard Polystyrene: F-128 (Mw1,090,000, Mn1,030,000), F-10 (Mw106,000, Mn103,000), F-4 as standard polystyrene using an HLC-8120GPC apparatus manufactured by Tosoh Corporation (Mw43,000, Mn42,700), F-2 (Mw17,200, Mn16,900), A-5000 (Mw6,400, Mn6,100), A-2500 (Mw2,800, Mn2,700), A A calibration curve using -300 (Mw453, Mn387) was prepared, and the number average molecular weight was measured as a polystyrene equivalent value. Column: TSKGEL SuperHM-H + H5000 + H4000 + H3000 + H2000 manufactured by Tosoh Corporation. Eluent: THF. Flow rate: 0.6 ml / min. Detection: UV (254 nm). Temperature: 40 ° C. Sample concentration: 0.1%. Injection volume: 10 μl.

<Mole content of imide skeleton in A>
It was calculated by calculation from the charged raw material ratio.

<N>
The value of n in the general formula (1) and the average value thereof were calculated from the number average molecular weight.

<Epoxy equivalent>
It was measured according to JIS K 7236 and expressed as a solid content converted value.

<Amount of saponifiable chlorine>
Measured according to JIS K 7242-2 and expressed as a solid content converted value.

<Infrared analysis>
JAS. IR measurement was carried out on the resin of Example 2 at FT / IR-460Plus, manufactured by CO JASCO Corporation. This IR chart is shown in FIG.

<Glass transition temperature and linear expansion coefficient of specific cured product>
(Production of specific cured product)
A specific cured product was prepared by the following curing method I.

Curing method I: Epoxy equivalent 5000 g / eq. The above (Examples 2 to 5, Comparative Example 2)
in the case of)
100 g of solid content of imide skeleton resin, 1 g of curing agent: jER Cure YLH129 (Japan Epoxy Resin Co., Ltd. trade name, bisphenol A novolac resin, hydroxyl group equivalent 117 (g / eq.), Softening point 115 (° C.)), Curing accelerator: 0.5 g of 2-ethyl-4-methylimidazole, 80 g of cyclohexane and 80 g of dimethylacetamide were mixed in a 1000 ml beaker, and a Teflon film (Nichias Co., Ltd.) using an applicator with a slit width of 300 μm. : Teflon tape TOMBO9001), a coating film was drawn on a hot air dryer at 170 ° C. for 30 minutes and further held at 200 ° C. for 90 minutes to obtain a specific cured product having a thickness of 60 to 100 μm.

(Measurement of glass transition temperature and linear expansion coefficient)
The glass transition temperature and linear expansion coefficient (average value at 30 to 130 ° C.) of the obtained specific cured product were measured by the following methods.
Using a TMA / SS6100 device manufactured by SII Nanotechnology Co., Ltd., in a film tension mode, from 20 ° C. to 250 ° C., 5 ° C./min. The average linear expansion coefficient and glass transition temperature of 30 ° C. to 130 ° C. were measured. A TMA chart of the specific cured product of Example 2 is shown in FIG.

  From the above results, it can be seen that the imide skeleton resin of the present invention is excellent in heat resistance and has a low linear expansion coefficient.

[Examples 6 to 9, Comparative Example 3]
Using the imide skeleton resin obtained in Examples 2 to 5 and Comparative Example 2 and a commercially available epoxy resin, a varnish was prepared at a blending ratio shown in Table 3, and a copper foil (F3-WS) was used using a 300 μm applicator. ) A coating film was drawn thereon and held at 170 ° C. for 30 minutes by a hot air dryer, and further held at 200 ° C. for 90 minutes to obtain a cured resin with a copper foil having a thickness of 60 to 100 μm.

  Separately, using a varnish with a blending ratio shown in Table 3, using a 300 μm applicator, a coating film was drawn on a copper foil (F3-WS), and kept at 170 ° C. for 30 minutes with a hot air dryer. A B-staged semi-cured resin with foil was prepared, and two sheets of this B-staged semi-cured resin with copper foil were superposed and held in a heating press machine at 200 ° C. and a pressure of 2.9 MPa for 90 minutes. It was created.

In addition, the commercially available epoxy resin, the hardening | curing agent, copper foil, etc. which were used are as follows.
jER 157S70: Japan Epoxy Resin Co., Ltd. trade name, bisphenol A type epoxy resin, epoxy equivalent 210 (g / eq.)
jER Cure YLH129: Japan Epoxy Resin Co., Ltd. trade name, bisphenol A novolak resin, hydroxyl group equivalent 117 (g / eq.), softening point 115 (° C.)
B103: Nippon Light Metal Co., Ltd. trade name, aluminum hydroxide, average particle size 8 μm
AroCy B-30: Huntsuman Co., Ltd. trade name, bisphenol A dicyanate resin F3-WS: Furukawa Circuit Foil Co., Ltd. trade name, electrolytic copper foil, thickness 18 μm

  The physical properties of the cured resin with copper foil thus obtained were measured by the following method. In addition, the laminated body was used for the measurement of copper foil peel strength, and the other physical property was measured only with the cured resin which peeled copper foil from the cured resin with copper foil. The results are shown in Table 3.

<Linear expansion coefficient and glass transition temperature>
Using a TMA / SS6100 device manufactured by SII Nanotechnology Co., Ltd., in a film tension mode, from 20 ° C. to 250 ° C., 5 ° C./min. The average linear expansion coefficient and glass transition temperature of 30 ° C. to 130 ° C. were measured.

<Water absorption rate>
An ESPEC EHS-211MD apparatus was used, and the water absorption value of the film was measured under measurement conditions of 85 ° C./85% RH / 168 hours.

<Copper foil peel strength>
It measured according to JIS C6481.

  From Table 3, it can be seen that a cured film using the imide skeleton resin of the present invention has a low coefficient of linear expansion and excellent heat resistance (glass transition temperature).

It is explanatory drawing of the buildup method. 3 is a GPC chart of an imide skeleton resin of Example 2. 4 is an IR chart of an imide skeleton resin of Example 2. 3 is a TMA chart of a specific cured product of an imide skeleton resin of Example 2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Inner layer circuit board 1A Circuit 2 Film 2A Copper foil 3 Film with copper foil

Claims (12)

Imide skeleton resin represented by the following general formula (1).

(In the formula, A is a linking group represented by the following general formula (2-1), the following general formula (3-1), or the following general formula (4-1), and n + 1 A's are the same as each other. However, 5 mol% or more in all the components A is a linking group represented by the following general formula (4-1).
B is Ru Oh a group represented by the Symbol structural formula (5).
n is an integer of 0-200 . )

(Wherein R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₁ may be the same as or different from each other. Two R ₁ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.
m is 0 or 1.
X is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —SO ₂ —, or CO—. )

(Wherein R ₂ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₂ may be the same as or different from each other. Two R ₂ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.

(Wherein R ₃ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₃ may be the same as or different from each other. Two R ₃ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.
R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a phenyl group, or a hydrocarbon group having 1 to 10 carbon atoms. )

The imide skeleton resin according to claim 1, wherein the linking group represented by the general formula (4-1) is represented by the following general formula (6-1).

(Wherein R ₇ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R ₇ may be the same as or different from each other. Two R ₇ bonded to adjacent carbon atoms on the ring may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.   In Claim 1 or 2, epoxy equivalent is 250 g / eq. An imide skeleton resin characterized by the above.   In any 1 item | term of Claim 1 thru | or 3, the glass transition temperature of the hardened | cured material which mix | blends only a hardening | curing agent and a hardening accelerator is 100 degreeC or more, and the linear expansion coefficient in below glass transition temperature is less than 75 ppm / degrees C. An imide skeleton resin characterized by being. A divalent phenol compound represented by any one of the following general formula (2-2), the following general formula (3-2), and the following general formula (4-2) is reacted with an epihalohydrin in the presence of an alkali. The method for producing an imide skeleton resin according to any one of claims 1 to 4, wherein:

(In the formula, R ₁ , X, and m are respectively synonymous with those in the general formula (2-1).)

(In the formula, R ₂ has the same meaning as in the general formula (3-1).)

(In formula, R < ₃ >, R < ₄ >, R < ₅ >, R < ₆ > is respectively synonymous with the said general formula (4-1).) A bifunctional epoxy resin represented by any one of the following general formula (7), the following general formula (8), and the following general formula (9), the following general formula (2-2), and the following general formula (3-2) And a dihydric phenol compound represented by any one of the following general formula (4-2) in the presence of a catalyst. Manufacturing method of imide skeleton resin.

(Wherein R ₁ and X have the same meanings as in the general formula (2-1), l is 0 or 1, and p is an integer of 0 to 10)

(In the formula, R ₂ has the same meaning as in formula (3-1). Q is an integer of 0 to 10.)

_{(Wherein, R 3, R 4, R} 5, R 6 , the .r synonymous as in each of the general formula (4-1) is an integer of 0.)

(In the formula, R ₁ , X, and m are respectively synonymous with those in the general formula (2-1).)

(In the formula, R ₂ has the same meaning as in the general formula (3-1).)

(In formula, R < ₃ >, R < ₄ >, R < ₅ >, R < ₆ > is respectively synonymous with the said general formula (4-1).)   A curable resin composition comprising the imide skeleton resin according to any one of claims 1 to 4.   8. The curable resin composition according to claim 7, further comprising a curing agent and a curing accelerator.   9. The method according to claim 7, further comprising one or more selected from the group consisting of epoxy resins other than the imide skeleton resin, thermosetting resins other than epoxy resins, and inorganic fillers. Curable resin composition.   The curable resin composition according to any one of claims 7 to 9, which is used for a printed wiring board.   A cured resin obtained by curing the curable resin composition according to any one of claims 7 to 10.   A laminate of the cured resin according to claim 11 and a conductive metal.

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