JP2019137622A - Polyester resin - Google Patents

Abstract

To provide a polyester resin that gives a cured product having a high elastic modulus, and also has excellent dielectric properties.SOLUTION: A polyester resin has, in its molecular structure, a structural site (A) represented by the following structural formula (X-1) or (X-2) and a plurality of aromatic ester structural sites (E), and has a softening point of 40-200°C.SELECTED DRAWING: None

Description

  The present invention relates to a polyester resin having a high elastic modulus and excellent dielectric characteristics in a cured product, a curable composition containing the polyester resin, a cured product thereof, a semiconductor sealing material using the curable composition, and a printed wiring board And a build-up film.

  In the technical field of insulating materials used for semiconductors, multilayer printed boards, and the like, development of new resin materials that meet these market trends is required as various electronic members become thinner and smaller. Specific required performance includes heat resistance and moisture absorption resistance in the cured product, copper foil adhesiveness, as well as low dielectric constant and dielectric loss tangent value in the cured product as a measure to increase the signal speed and frequency, It is also important that there is no change in physical properties such as glass transition temperature (Tg) as reliability under high temperature conditions, and that the cured product has a high elastic modulus and low cure shrinkage as a countermeasure against warping and distortion associated with thinning. is there.

  As a resin material having a relatively low dielectric constant and dielectric loss tangent in a cured product, a technique using an active ester resin obtained by esterifying dicyclopentadiene phenol resin and α-naphthol with phthalic acid chloride as a curing agent for an epoxy resin. It is known (see Patent Document 1 below). The active ester resin described in Patent Document 1 has a low dielectric constant and dielectric loss tangent in a cured product as compared with the case where a conventional curing agent such as a phenol novolac resin is used. However, the value of the dielectric loss tangent has been required to be further reduced. Further, the elastic modulus of the cured product is low, and it cannot cope with the reduction in thickness and size of various electronic members.

JP 2004-169021 A

  Accordingly, the problem to be solved by the present invention is to use a polyester resin having a high elastic modulus in a cured product and excellent in dielectric properties, a curable composition containing the polyester resin, a cured product thereof, and the curable composition. It is providing a semiconductor sealing material, a printed wiring board, and a buildup film.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyester resin having a phenolphthalein structure or a similar chemical structure in the molecular structure has a high elastic modulus in a cured product and excellent dielectric properties. As a result, the present invention has been completed.

  That is, the present invention has a structural site (A) represented by the following structural formula (X-1) or (X-2) and a plurality of aromatic ester structural sites (E) in the molecular structure. Further, the present invention relates to a polyester resin having a softening point in the range of 40 to 200 ° C.

（式中Ｒ^１、Ｒ^２はそれぞれ独立に脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基、アラルキル基の何れかである。ｌ、ｍはそれぞれ独立に０又は１〜４の整数である。Ｒ^３は脂肪族炭化水素基又は置換基を有していてもよいアリール基である。）

(Wherein R ¹ and R ² are each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group. L and m are each independently 0 or 1 to 1; 4 is an integer of 4. R ³ is an aliphatic hydrocarbon group or an aryl group which may have a substituent.

  The present invention further relates to a curable composition containing the polyester resin and a curing agent.

  The present invention further relates to a cured product of the curable composition.

  The present invention further relates to a semiconductor sealing material using the curable composition.

  The present invention further relates to a printed wiring board using the curable composition.

  The present invention further relates to a build-up film using the curable composition.

  According to the present invention, a polyester resin having a high modulus of elasticity and excellent dielectric properties in a cured product, a curable composition containing the polyester resin, a cured product thereof, a semiconductor sealing material using the curable composition, and a print A wiring board and a build-up film can be provided.

1 is a GPC chart of the polyester resin (1) obtained in Example 1. FIG. FIG. 2 is a GPC chart of the polyester resin (2) obtained in Example 2.

Hereinafter, the present invention will be described in detail.
The polyester resin of the present invention has a structural part (A) represented by the following structural formula (X-1) or (X-2) and a plurality of aromatic ester structural parts (E) in the molecular structure. The softening point is in the range of 40 to 200 ° C.

（式中Ｒ^１、Ｒ^２はそれぞれ独立に脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基、アラルキル基の何れかである。ｌ、ｍはそれぞれ独立に０又は１〜４の整数である。Ｒ^３は水素原子、脂肪族炭化水素基、又は置換基を有していてもよいアリール基である。）

(Wherein R ¹ and R ² are each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group. L and m are each independently 0 or 1 to 1; 4 is an integer of 4. R ³ is a hydrogen atom, an aliphatic hydrocarbon group, or an aryl group which may have a substituent.

In the structural formulas (X-1) and (X-2), R ¹ and R ² are each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group. is there. The aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, vinyl group, allyl group, methallyl group, 1-propenyl Group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural site in which the aromatic hydrocarbon group, the alkoxy group, the halogen atom, or the like is substituted on the aromatic nucleus. Examples of the aryloxy group include a phenyloxy group, a naphthyloxy group, an anthryloxy group, and a structural site obtained by substituting the aliphatic hydrocarbon group, alkoxy group, halogen atom or the like on the aromatic nucleus. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a structural site obtained by substituting the aliphatic hydrocarbon group, an alkoxy group, a halogen atom, or the like on these aromatic nuclei. Among these, an aliphatic hydrocarbon group having 1 to 4 carbon atoms is preferable from the viewpoint of the elastic modulus and dielectric properties of the cured product, curability with a curing agent, and the like. More preferably, l and m are 0.

R ³ in the structural formula (X-2) is an aliphatic hydrocarbon group or an aryl group which may have a substituent. The aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, vinyl group, allyl group, methallyl group, 1-propenyl Group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group and the like. The aryl group that may have the substituent includes a phenyl group, a naphthyl group, an anthryl group, and a structural site in which the aromatic hydrocarbon group, the alkoxy group, the halogen atom, or the like is substituted on the aromatic nucleus. Can be mentioned. The number of substituents on the aryl group is not particularly limited, and may have two or more substituents. Especially, it is preferable that it is an aryl group which may have a substituent from viewpoints, such as an elasticity modulus and dielectric property in hardened | cured material. When the substituent on the aryl group is an aliphatic hydrocarbon group, the number of carbon atoms is preferably in the range of 1 to 4.

  In the polyester resin of the present invention, the structural moiety (A) represented by the structural formula (X-1) or (X-2) may exist as a residue of a dihydroxy compound, a dicarboxylic acid compound or It may exist as a residue of the derivative. Further, the structural site (A) present in the polyester resin may all have the same structure, or a plurality of types of structural sites may coexist.

  The aromatic ester structure site (E) refers to an ester bond site formed from a hydroxyl group bonded to an aromatic ring and a carboxy group bonded to the aromatic ring. Such an aromatic ester structure site (E) has a high reaction activity with a curing agent such as an epoxy resin.

  The polyester resin of the present invention preferably has an aryloxycarbonyl structure (P) or an arylcarbonyloxy structure (A) at the molecular end from the viewpoint of dielectric properties in the cured product. Specific examples of the aryloxycarbonyl structure (P) include a structural moiety represented by the following structural formula (P). In addition, specific examples of the arylcarbonyloxy structure (A) include a structural moiety represented by the following structural formula (A).

［式中Ａｒは置換基を有していてもよいアリール基である。］

[In the formula, Ar is an aryl group which may have a substituent. ]

Examples of the aryl group which may have a substituent in the structural formulas (P) and (A) include a phenyl group, a naphthyl group, an anthryl group, and the aliphatic hydrocarbon group, alkoxy on the aromatic nucleus thereof. And a structural site substituted with a group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group, and the like. Specific examples of these substituents include those exemplified as R ¹ and R ^{2 in the} structural formulas (X-1) and (X-2). The number of substituents on the aryl group is not particularly limited, and may have two or more substituents. Especially, since it becomes an active ester compound which is excellent also in the mixability with a hardening | curing agent and another resin component in addition to various physical properties of hardened | cured material, it is preferable that it is a naphthyl group which may have a substituent. The substituent on the naphthyl group is preferably an aliphatic hydrocarbon group, an alkoxy group or a halogen atom, and the aliphatic hydrocarbon group preferably has 1 to 4 carbon atoms.

  Since the polyester resin of the present invention is excellent in balance between curability and various performances in a cured product, the functional group equivalent is preferably in the range of 150 to 350 g / equivalent. In the present invention, the functional group in the polyester resin means an ester bond site and a phenolic hydroxyl group in the polyester resin. The functional group equivalent of the polyester resin is a value calculated from the charged amount of the reaction raw material.

  The polyester resin of the present invention is excellent in the balance of elastic modulus, dielectric properties, moisture and heat resistance, and other performances in the cured product, so that the acid value and the hydroxyl value are preferably 10 mgKOH / g or less, and 5 mgKOH / g or less. More preferably.

  One feature of the polyester resin of the present invention is that the softening point is in the range of 40 to 200 ° C. When the softening point is within this range, the polyester resin is excellent in reactivity with a curing agent such as an epoxy resin and can be used as a curable composition. Furthermore, in addition to the above matters, it is excellent in fluidity at the time of heat molding required for a semiconductor encapsulant, a printed wiring board prepreg, and a build-up film, so that its softening point is in the range of 50 to 180 ° C. preferable. In the present invention, the softening point of the resin is a value measured based on JIS K7234.

  The polyester resin of the present invention has a structural site (A) represented by the structural formula (X-1) or (X-2) and a plurality of aromatic ester structural sites (E), and has a softening point. If it is the range of 40-200 degreeC, another specific structure will not be specifically limited, A wide variety of structures can be taken. Specific examples of the polyester resin of the present invention include the following polyester resins (I) to (IV). These are merely examples of the polyester resin, and the polyester resin of the present invention is not limited to this. Moreover, a polyester resin may be used individually by 1 type, and may use 2 or more types together.

  Polyester resin (I): an esterified product of an aromatic monohydroxy compound (a1), an aromatic polycarboxylic acid or its acid halide (a2), and a compound (a3) having two or more phenolic hydroxyl groups in the molecular structure. A polyester resin in which the compound (a3) is a compound represented by the following structural formula (x1) or (x2) as an essential component

（式中Ｒ^１、Ｒ^２はそれぞれ独立に脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基、アラルキル基の何れかである。ｌ、ｍはそれぞれ独立に０又は１〜４の整数である。Ｒ^３は水素原子、脂肪族炭化水素基又は置換基を有していてもよいアリール基である。）

(Wherein R ¹ and R ² are each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group. L and m are each independently 0 or 1 to 1; 4 is an integer of 4. R ³ is a hydrogen atom, an aliphatic hydrocarbon group or an aryl group which may have a substituent.

  Polyester resin (II): an esterified product of a monohydroxy compound (a1), an aromatic polycarboxylic acid or an acid halide thereof (a2), and a compound (a3) having two or more phenolic hydroxyl groups in the molecular structure, The polyester resin in which the compound (a2) is a compound represented by the following structural formula (x3) or (x4) as an essential component

（式中Ｒ^１、Ｒ^２はそれぞれ独立に脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基、アラルキル基の何れかである。ｌ、ｍはそれぞれ独立に０又は１〜４の整数である。Ｒ^３は水素原子、脂肪族炭化水素基又は置換基を有していてもよいアリール基である。Ｙは水素原子又はハロゲン原子である。）

(Wherein R ¹ and R ² are each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group. L and m are each independently 0 or 1 to 1; 4 is an integer of 4. R ³ is a hydrogen atom, an aliphatic hydrocarbon group or an aryl group which may have a substituent, and Y is a hydrogen atom or a halogen atom.)

  Polyester resin (III): aromatic polycarboxylic acid or its acid halide (a2), compound (a3) having two or more phenolic hydroxyl groups in the molecular structure, and aromatic monocarboxylic acid or its acid halide (a4) A polyester resin in which the compound (a3) is an essential component of the compound represented by the structural formula (x1) or (x2)

  Polyester resin (IV): aromatic polycarboxylic acid or acid halide thereof (a2), compound having two or more phenolic hydroxyl groups in the molecular structure (a3), and aromatic monocarboxylic acid or acid halide thereof (a4) A polyester resin in which the compound (a2) is an essential component of the compound represented by the structural formula (x3) or (x4)

Among the polyester resins (I) to (IV), the polyester resin (I) or (II) is preferable because the dielectric constant and dielectric loss tangent of the cured product are further reduced. Further, the polyester resin (I) is particularly preferable because the reaction raw materials are easily available. In the structural formulas (x1) to (x4), R ¹ , R ² , R ³ , l, and m are the same as those in the structural formulas (X-1) and (X-2).

Hereinafter, each reaction raw material of the polyester resin (I) will be described.
Specific examples of the aromatic monohydroxy compound (a1) include phenols or phenol compounds having one or more substituents on the aromatic nucleus of phenol, naphthol or one or more substituents on the aromatic nucleus of naphthol. And anthracenol compounds having one or more substituents on the aromatic nucleus of anthracenol. Examples of the substituent on the aromatic nucleus include the aliphatic hydrocarbon group, alkoxy group, halogen atom, aryl group, aryloxy group, aralkyl group and the like, and specific examples thereof are the structural formulas (X-1), ( Examples thereof include those exemplified as R ¹ and R ^{2 in} X-2). One type of aromatic monohydroxy compound (a1) may be used alone, or two or more types may be used in combination.

  Among these, since it becomes a polyester resin excellent in various properties such as heat resistance and reactivity in addition to the elastic modulus and dielectric properties in the cured product, one or more substituents are added on the aromatic nucleus of naphthol or naphthol. A naphthol compound having is more preferable. The substituent on the aromatic nucleus is preferably an aliphatic hydrocarbon group, an alkoxy group or a halogen atom, and the aliphatic hydrocarbon group preferably has 1 to 4 carbon atoms.

Examples of the aromatic polycarboxylic acid or its acid halide (a2) include benzenedicarboxylic acids such as isophthalic acid and terephthalic acid; benzenetricarboxylic acids such as trimellitic acid; naphthalene-1,4-dicarboxylic acid and naphthalene-2 , 3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene dicarboxylic acid such as naphthalene-2,7-dicarboxylic acid; these acid halides; having one or more substituents on these aromatic nuclei Compounds and the like. Examples of the acid halide include acid chlorides, acid bromides, acid fluorides, and acid iodides. In addition, examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group, and the like, and specific examples thereof are the structural formula (X-1), What was illustrated as R < ¹ >, R < ² > in (X-2) etc. are mentioned. The aromatic polycarboxylic acid or its acid halide (a2) may be used alone or in combination of two or more.

  Among these, since it becomes a polyester resin excellent in various properties such as heat resistance and reactivity in addition to the elastic modulus and dielectric properties in the cured product, benzenedicarboxylic acid such as isophthalic acid and terephthalic acid or its acid halide is used. preferable.

  The compound (a3) having two or more phenolic hydroxyl groups in the molecular structure is an essential component of the compound represented by the structural formula (x1) or (x2) (hereinafter referred to as “compound (X)”). To do. In particular, the ratio of the compound (X) in the compound (a3) is 50% by mass or more because the cured product produced by the present invention has a high modulus of elasticity and a more effective effect on dielectric properties. It is preferably 80% by mass or more.

  In addition, examples of the compound (a3) having two or more phenolic hydroxyl groups in the molecular structure that can be used in combination with the compound (X) include various aromatic polyhydroxy compounds and the aromatic monohydroxy compounds (a1). ) Novolak type resin using one kind or plural kinds of reaction raw materials, one kind or plural kinds of the aromatic monohydroxy compound (a1) and the following structural formulas (z-1) to (z-5)

［式中ｈは０又は１である。Ｒ^４はそれぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基、アラルキル基の何れかであり、ｉは０又は１〜４の整数である。Ｗはビニル基、ハロメチル基、ヒドロキシメチル基、アルキルオキシメチル基の何れかである。Ｖは炭素原子数１〜４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。ｊは１〜４の整数である。］
の何れかで表される化合物（ｚ）とを必須の反応原料とする反応生成物等が挙げられる。

[In the formula, h is 0 or 1. R ⁴ is each independently an aliphatic hydrocarbon group, alkoxy group, halogen atom, aryl group, aryloxy group, or aralkyl group, and i is an integer of 0 or 1 to 4. W is any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. V is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group. j is an integer of 1-4. ]
And reaction products using the compound (z) represented by any of the above as an essential reaction raw material.

R ⁴ in the structural formulas (z-1) to (z-5) is an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group. Examples include those exemplified as R ¹ and R ^{2 in} Structural Formulas (X-1) and (X-2).

The various aromatic polyhydroxy compounds include, for example, dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, polyhydroxybiphenyl, polyhydroxy In addition to (hydroxyphenyl) alkane, other bisphenol compounds, and the like, compounds having one or more substituents on the carbon atom of these compounds may be mentioned. Examples of the substituent on the carbon atom include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group, and the like, and specific examples thereof are the structural formulas (X-1) and (X -2) and those exemplified as R ¹ and R ^{2 in the} above.

  These polyester resins of the present invention can be produced, for example, by a method in which each reaction raw material is mixed and stirred under a temperature condition of about 40 to 65 ° C. in the presence of an alkali catalyst. You may perform reaction in an organic solvent as needed. Further, after completion of the reaction, the reaction product may be purified by washing with water or reprecipitation.

  Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. These may be used alone or in combination of two or more. Further, it may be used as an aqueous solution of about 3.0 to 30%. Among these, sodium hydroxide or potassium hydroxide having high catalytic ability is preferable.

  Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; and carbitols such as cellosolve and butyl carbitol. Examples include solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. These may be used alone or as a mixed solvent of two or more.

  The reaction ratio of each reaction raw material is appropriately adjusted according to the desired physical properties of the polyester resin to be obtained, and is particularly preferably as follows in the polyester resin (I). In the production of the polyester resin (I), the aromatic monohydroxy compound (a1), the aromatic polycarboxylic acid or its acid halide (a2), and a compound having two or more phenolic hydroxyl groups in the molecular structure ( The reaction ratio of a3) is the ratio of the number of moles of hydroxyl group of the aromatic monohydroxy compound (a1) and the number of moles of hydroxyl group of the compound (a3) having two or more phenolic hydroxyl groups in the molecular structure. The ratio is preferably 25/75 to 85/15, and more preferably 35/65 to 75/25. Moreover, a phenolic hydroxyl group is added to the aromatic monohydroxy compound (a1) and the molecular structure with respect to a total of 1 mol of the carboxyl group or acid halide group of the aromatic polycarboxylic acid or acid halide (a2) thereof. The total of the hydroxyl groups possessed by the compound (a3) having two or more is preferably in the range of 0.9 to 1.1 mol.

  When the polyester resin of the present invention is the polyester resin (I), it becomes a polyester resin excellent in various properties such as heat resistance and reactivity in addition to the elastic modulus and dielectric properties in the cured product. The following structural formula (1)

［式中Ｘは前記構造式（Ｘ−１）又は（Ｘ−２）で表される構造部位である。Ａｒ^１は置換基を有していてもよいアリーレン基、Ａｒ^２は置換基を有していてもよいアリール基である。］
で表される化合物を含有することが好ましい。また、ポリエステル樹脂中の当該化合物の含有量は、１０〜５０％の範囲であることが好ましく、１５〜４５％の範囲であることがより好ましい。

[Wherein X is a structural moiety represented by the structural formula (X-1) or (X-2). Ar ¹ is an arylene group which may have a substituent, and Ar ² is an aryl group which may have a substituent. ]
It is preferable to contain the compound represented by these. Further, the content of the compound in the polyester resin is preferably in the range of 10 to 50%, more preferably in the range of 15 to 45%.

  Furthermore, the polyester resin of the present invention is a compound represented by the following structural formula (2), that is, a diester of the aromatic polycarboxylic acid or its acid halide (a2) and the aromatic monohydroxy compound (a1). It is preferable to contain a compound. The content of the compound in the polyester resin is preferably in the range of 5 to 65%, more preferably in the range of 10 to 55%.

［式中Ａｒ^１は置換基を有していてもよいアリーレン基、Ａｒ^２は置換基を有していてもよいアリール基である。］

[In the formula, Ar ¹ represents an arylene group which may have a substituent, and Ar ² represents an aryl group which may have a substituent. ]

  The content of the compound represented by the structural formula (1) in the polyester resin is a value calculated from the area ratio of the GPC chart measured under the following conditions.

Measuring device: “HLC-8320 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G4000HXL”
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: “GPC workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8320”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids, filtered through a microfilter (50 μl)

Ar ¹ in the structural formula (1) is a phenylene group, a naphthylene group, an anthrylene group, and the aliphatic hydrocarbon group, alkoxy group, halogen atom, aryl group, aryloxy group, aralkyl group, etc. on these aromatic nuclei. The structural site | part etc. which were substituted are mentioned. Specific examples of these substituents include those exemplified as R ¹ and R ^{2 in the} structural formulas (X-1) and (X-2). Ar ¹ is more specifically the residue of the aromatic polycarboxylic acid or acid halide (a2) thereof. Accordingly, a phenylene group is preferable.

Ar ² in the structural formula (1) is a phenyl group, a naphthyl group, an anthryl group, and the aromatic hydrocarbon group, alkoxy group, halogen atom, aryl group, aryloxy group, aralkyl on these aromatic nuclei. Examples include structural sites substituted with groups and the like. Specific examples of these substituents include those exemplified as R ¹ and R ^{2 in the} structural formulas (X-1) and (X-2). Ar ² is more specifically a residue of the aromatic monohydroxy compound (a1). Therefore, it is preferably a naphthyl group which may have a substituent. The substituent on the naphthyl group is preferably an aliphatic hydrocarbon group, an alkoxy group or a halogen atom, and the aliphatic hydrocarbon group preferably has 1 to 4 carbon atoms.

  The curable composition of this invention contains the said polyester resin and a hardening | curing agent. The curing agent may be a compound that can react with the polyester resin of the present invention, and various compounds can be used without any particular limitation. An example of the curing agent is an epoxy resin. Examples of the epoxy resin include polyglycidyl ether of a compound (a3) having two or more phenolic hydroxyl groups in the molecular structure. More specifically, bisphenol type epoxy resin; biphenyl type epoxy resin; various novolak type epoxy resins made from phenol, cresol, naphthol, biphenol, bisphenol, etc .; triphenolmethane type epoxy resin; dicyclopentadiene-phenol addition Reaction type epoxy resin; Polyarylene ether type epoxy resin; Polyglycidyl ether of phenol resin having a resin structure in which phenol, cresol, naphthol, biphenol, bisphenol and the like are connected by an arylene alkylene group.

  In the curable composition of the present invention, the blending ratio of the polyester resin and the curing agent is not particularly limited and can be appropriately adjusted according to the desired performance of the cured product. As an example of the blending in the case of using an epoxy resin as a curing agent, a ratio in which the total of functional groups in the polyester resin is 0.7 to 1.5 mol with respect to a total of 1 mol of epoxy groups in the epoxy resin. It is preferable that

  When an epoxy resin is used as the curing agent, various compounds used as a general curing agent for epoxy resins may be used in combination. Specific examples thereof include amine compounds, amide compounds, acid anhydrides, phenol resins, and active ester resins other than the polyester resin of the present invention. When these are used, since the effect of the present invention is sufficiently exhibited, the ratio of the polyester resin of the present invention is 30% by mass or more with respect to the total mass of the epoxy resin curing agent containing the polyester resin of the present invention. Is preferable, and it is more preferable that it is 50 mass% or more.

The epoxy resin curing agent is not particularly limited as long as it causes a curing reaction with the epoxy resin, and various types can be used. Specific examples thereof include amine compounds, amide compounds, acid anhydrides, phenol resins, and active ester resins. These may be used alone or in combination of two or more. Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide, aliphatic dibasic acid, dimer acid, polyamide resin synthesized from a carboxylic acid compound of fatty acid and an amine such as ethylenediamine. Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride. Examples of the phenol resin include various novolak resins, triphenolmethane type resins, dicyclopentadiene addition type phenol resins, polyarylene ether type phenol resins, phenols and cresols made from phenol, cresol, naphthol, biphenol, bisphenol and the like. , Phenol resin having a resin structure in which naphthol, biphenol, bisphenol and the like are connected by an arylene alkylene group. Examples of the active ester resin include an esterified product of the phenol resin and an aromatic dicarboxylic acid and a phenolic hydroxyl group-containing compound, an esterified product of an aromatic dicarboxylic acid and a phenolic hydroxyl group-containing compound, and the like. These may be used alone or in combination of two or more.

  The blending ratio of the polyester resin, epoxy resin, and other epoxy resin curing agent of the present invention is the functionality in the polyester resin and other epoxy resin curing agent with respect to a total of 1 mol of epoxy groups in the epoxy resin. It is preferable that the total amount of groups be 0.7 to 1.5 mol.

  In addition to this, the curable composition of the present invention may contain a cyanate ester resin, a benzoxazine resin, a polyphenylene ether resin, an acrylic resin, a polyphosphate ester, a phosphate ester-carbonate copolymer, and the like. These may be used alone or in combination of two or more.

  The curable composition of this invention may contain various additives, such as a hardening accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, an emulsifier, as needed.

  Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, Lewis acids, amine complex salts, and the like. Among them, from the viewpoint of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc., triphenylphosphine for phosphorus compounds, 1,8-diazabicyclo- [5.4.0] -undecene (DBU for tertiary amines). ), 2-ethyl-4-methylimidazole is preferred for imidazole compounds, and 4-dimethylaminopyridine is preferred for pyridine compounds.

  The flame retardant is, for example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, inorganic phosphorus compounds such as phosphate amide; phosphate ester compound, phosphonic acid Compound, phosphinic acid compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) ) Cyclic organic phosphorus such as -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide Compound, and compound such as epoxy resin and phenol resin Organic phosphorus compounds such as reacted derivatives; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazines; silicone-based flame retardants such as silicone oil, silicone rubber and silicone resin; metal hydroxides, metals Examples thereof include inorganic flame retardants such as oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. When using these flame retardants, it is preferable that it is the range of 0.1-20 mass% in a curable composition.

  The said inorganic filler is mix | blended, for example when using the curable composition of this invention for a semiconductor sealing material use. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Especially, since it becomes possible to mix | blend more inorganic fillers, the said fused silica is preferable. The fused silica can be used in either crushed or spherical shape, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the curable composition, a spherical one is mainly used. It is preferable. Furthermore, in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable composition.

  In addition, when using the curable composition of this invention for uses, such as an electrically conductive paste, electrically conductive fillers, such as silver powder and copper powder, can be used.

  As described in detail above, the polyester resin of the present invention has the characteristics that the cured product has a high elastic modulus and excellent dielectric properties. In addition, the general required performance required for resin materials, such as solubility in general-purpose organic solvents, curability with epoxy resins, moisture absorption resistance, storage stability, and adhesion to bases, is sufficiently high. In addition to electronic materials such as printed wiring boards, semiconductor sealing materials, and resist materials, it can be widely used for applications such as paints, adhesives, and molded products.

  When using the curable composition of this invention for a printed wiring board use or a buildup adhesive film use, generally it is preferable to mix | blend and dilute and use an organic solvent. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like. The type and blending amount of the organic solvent can be adjusted as appropriate according to the environment in which the curable composition is used. For example, for printed wiring board applications, the solvent must be a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, or dimethylformamide. It is preferable to use it in a proportion that the nonvolatile content is 40 to 80% by mass. For build-up adhesive film applications, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, carbitols such as cellosolve, butyl carbitol, etc. It is preferable to use a solvent, an aromatic hydrocarbon solvent such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like, and it is preferable to use the nonvolatile component in a proportion of 30 to 60% by mass.

  Moreover, the method of manufacturing a printed wiring board using the curable composition of the present invention includes, for example, impregnating a curable composition into a reinforcing base material and curing it to obtain a prepreg, and heating this with a copper foil. The method of making it crimp is mentioned. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. Although the impregnation amount of the curable composition is not particularly limited, it is usually preferable to prepare so that the resin content in the prepreg is 20 to 60% by mass.

  When using the curable composition of this invention for a semiconductor sealing material use, generally it is preferable to mix | blend an inorganic filler. The semiconductor sealing material containing the polyester resin of the present invention, a curing agent, an inorganic filler, and other optional components can be prepared by mixing the compound using, for example, an extruder, a kneader, a roll, and the like. . A method for molding a semiconductor package using the obtained semiconductor sealing material is, for example, molding the semiconductor sealing material using a casting or transfer molding machine, an injection molding machine, etc., and a temperature of 50 to 200 ° C. The method of heating for 2 to 10 hours under conditions is mentioned, By such a method, the semiconductor device which is a molding can be obtained.

  Next, the present invention will be specifically described with reference to examples and comparative examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.

  The GPC measurement conditions in this example are as follows.

Measuring device: “HLC-8320 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G4000HXL”
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: “GPC workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8320”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids, filtered through a microfilter (50 μl)

Example 1 Production of Polyester Resin (1) Into a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 197 g of a compound represented by the following structural formula (a), 288 g of 1-naphthol, toluene 2000 g was charged, and the contents were dissolved while the inside of the flask was purged with nitrogen under reduced pressure. Next, 305 g of isophthalic acid chloride was charged, and the contents were dissolved while the inside of the flask was purged with nitrogen under reduced pressure. 1.0 g of tetrabutylammonium bromide was added and dissolved, and the inside of the system was controlled to 60 ° C. or lower while performing nitrogen gas purge, and 600 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued for another hour. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and the mixture was stirred and mixed for about 15 minutes, and then allowed to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and then dried under heating and reduced pressure conditions to obtain a polyester resin (1). The functional group equivalent of the polyester resin (1) was 226 g / equivalent, and the softening point measured based on JIS K7234 was 117 ° C. In the polyester resin (1), the content of the component corresponding to the compound represented by the structural formula (1) was 41.8% as a value calculated from the area ratio of the GPC chart. The content of the component corresponding to the diester compound represented by the structural formula (2) was 37.4% as a value calculated from the area ratio of the GPC chart. A GPC chart of the polyester resin (1) is shown in FIG.

Example 2 Production of Active Ester Compound (2) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 159 g of phenolphthalein, 288 g of 1-naphthol, and 2000 g of toluene. The contents were dissolved while substituting with nitrogen under reduced pressure. Next, 305 g of isophthalic acid chloride was charged, and the contents were dissolved while the inside of the flask was purged with nitrogen under reduced pressure. 1.0 g of tetrabutylammonium bromide was added and dissolved, and the inside of the system was controlled to 60 ° C. or lower while performing nitrogen gas purge, and 600 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued for another hour. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and the mixture was stirred and mixed for about 15 minutes, and then allowed to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and then dried under heating under reduced pressure to obtain a polyester resin (2). The functional group equivalent of the polyester resin (2) was 214 g / equivalent, and the softening point measured based on JIS K7234 was 114 ° C. In the polyester resin (2), the content of the component corresponding to the compound represented by the structural formula (1) was 30.6% as a value calculated from the area ratio of the GPC chart. The content of the component corresponding to the diester compound represented by the structural formula (2) was 43.2% as calculated from the area ratio in the GPC chart. A GPC chart of the polyester resin (2) is shown in FIG.

Production Example 1 Production of Polyester Resin (1 ′) A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 72 g of 1-naphthol, dicyclopentadiene addition type phenol resin (“JFE Chemical” -DPP-85 ", softening point 86 ° C, hydroxyl group equivalent: 165 g / equivalent) 165 g, isophthalic acid chloride 152 g and toluene 1000 g were charged, and the inside of the system was purged with nitrogen under reduced pressure to dissolve. While dissolving 0.5 g of tetrabutylammonium bromide and performing a nitrogen gas purge, the inside of the system was controlled to 60 ° C. or lower, and 310 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued for another hour. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. 330 g of water was added to the remaining organic layer, and the mixture was stirred and mixed for about 15 minutes, and then allowed to stand for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7, and then dried under heating and reduced pressure conditions to obtain 330 g of a polyester resin (1 ′). The functional group equivalent of the polyester resin (1 ′) was 223 g / equivalent, and the softening point measured based on JIS K7234 was 150 ° C.

Examples 3 and 4 and Comparative Example 1
The curable composition was adjusted in the following manner, and various evaluation tests were performed. The results are shown in Table 1.

Manufacture of curable composition Polyester resin, an epoxy resin, and dimethylaminopyridine (DMAP) were mix | blended according to the mixing | blending of the following Table 1, and the curable composition was obtained.

Preparation of cured product The curable composition was poured into a 11 cm × 9 cm × 2.4 mm mold and molded at 180 ° C. for 20 minutes using a press. The molded product was taken out from the mold and further cured at 175 ° C. for 5 hours to obtain a cured product.

Measurement of Elastic Modulus A test piece having a size of width 5 mm × length 54 mm × thickness 2.4 mm was cut out from the cured product. Using a viscoelasticity measuring device (“solid viscoelasticity measuring device RSAII” manufactured by Rheometric Co., Ltd.), a test piece 40 was measured by DMA (dynamic viscoelasticity) measurement by a rectangular tension method (frequency 1 Hz, temperature rising temperature 3 ° C./min). The storage modulus at 0 ° C. was measured.

Dissipation factor measurement

Measurement of dielectric constant and dielectric loss tangent Cured material stored in a room at 23 ° C and 50% humidity for 24 hours after heating and vacuum drying using the impedance material analyzer "E8362C" manufactured by Agilent Technologies, Inc. The dielectric loss tangent value was measured. Measurement was performed under two conditions of 1 GHz and 10 GHz, and the difference between the two values (10 GHz measurement value-1 GHz measurement value) was evaluated as frequency dependence.

(*) Epoxy resin: “EPICLON 850-S” manufactured by DIC Corporation, bisphenol A type epoxy resin, epoxy group equivalent is 188 g / equivalent

Claims (9)

In the molecular structure, it has a structural site (A) represented by the following structural formula (X-1) or (X-2) and a plurality of aromatic ester structural sites (E), and the softening point is 40 to 40. A polyester resin having a temperature range of 200 ° C.

(Wherein R ¹ and R ² are each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group. L and m are each independently 0 or 1 to 1; 4 is an integer of 4. R ³ is a hydrogen atom, an aliphatic hydrocarbon group or an aryl group which may have a substituent. The following structural formula (1)

[Wherein X is a structural moiety represented by the structural formula (X-1) or (X-2). Ar ¹ is an arylene group which may have a substituent, and Ar ² is an aryl group which may have a substituent. ]
The polyester resin according to claim 1, wherein the content of the compound represented by the formula is in the range of 10 to 50%. The polyester resin according to claim 2, wherein Ar ² is an optionally substituted naphthyl group. An esterified product of an aromatic monohydroxy compound (a1), an aromatic polycarboxylic acid or an acid halide thereof (a2), and a compound (a3) having two or more phenolic hydroxyl groups in the molecular structure, the compound (a3 2) The polyester resin according to claim 1, wherein a compound represented by the following structural formula (x1) or (x2) is an essential component.

(Wherein R ¹ and R ² are each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group. L and m are each independently 0 or 1 to 1; 4 is an integer of 4. R ³ is a hydrogen atom, an aliphatic hydrocarbon group or an aryl group which may have a substituent. A curable composition containing the polyester resin according to any one of claims 1 to 4 and a curing agent. A cured product of the curable composition according to claim 5. The semiconductor sealing material using the curable composition of Claim 5. A printed wiring board using the curable composition according to claim 5. A build-up film using the curable composition according to claim 5.

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