JP2012007018A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition that accepts electric components of next-generation specifications and has excellent heat resistance and storage stability.SOLUTION: The thermosetting resin composition comprises: an epoxy resin (A); a resin (B) having a carbonate skeleton, a urethane skeleton and an imide skeleton; a multifunctional phenol resin (C); and an amine compound (D) having bioactive effect.

Description

  The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition having excellent heat resistance useful as an adhesive for an electronic member or the like and a protective film.

In the electronics industry, electronic materials, electronic members, and mounting methods used for them are evolving due to increasing demands for light and thin electronic devices accompanying the miniaturization of semiconductor integrated circuits.
For example, phenolic resin has been mainly used for resin compositions used for color television mounting boards 40 years ago for reasons of excellent electrical insulation, but now it is modified by increasing the density of mounting boards. Alternatively, a composite material in which a thermoplastic or thermosetting resin component is copolymerized or blended with a polyfunctional epoxy resin and filled with several kinds of inorganic fillers is mainly used.

  On the other hand, applications that require unprecedented flexibility and connection reliability (FPC (Flexible Circuit Board), TAB (Tape Automated Bonding), COF (Chip On Film)) are emerging due to the evolution of mounting methods. Conventional insulating materials have a rigid chemical structure, so it was difficult to find an electronic material suitable for such applications. However, by introducing a chemical structure of thermoplastic resin or rubber component into the insulating material, the elastic modulus was reduced. The intended resin composition, an electronic member in which the resin composition is in the form of a film, and the like have been proposed.

As such a resin composition, a resin composition of an epoxy resin and a modified polyamideimide resin into which an alkylene group has been introduced has been proposed, which allows flexibility (reduction in elastic modulus) without reducing heat resistance and reliability. Has been achieved (for example, see Patent Document 1).
In addition, an anisotropic conductive resin composition in the form of a film is proposed in which conductive particles (gold plated coating of styrene) are dispersed in a toluene solution as a resin composition with epoxy resin, nitrile rubber, alkylphenol resin, and the like. Thus, adhesion to the FPC and connection reliability are obtained (see, for example, Patent Document 2).

However, in recent years, due to the demand for further miniaturization (design rule 0.032 μm) for the next generation and narrower pitch of the substrate circuit, it is clear that the heat-resistant operation guarantee temperature will be 30 ° C. or higher depending on the application. Thus, when electronic components are examined in the next generation specifications, even with resin compositions that have been put into practical use, there has been a problem of insufficient heat resistance.
In addition, as a result of globalization and production bases scattered all over the world due to the reorganization of the electronic parts industry since the 1990s, it is also necessary to consider storage stability such as long-term transportation.
In addition, it is known to use a block carboxylic acid for improving the storage stability of the epoxy resin composition (see, for example, Patent Document 3).

JP 2002-146325 A JP 05-217617 A JP 2004-75914 A

  In view of the current situation, an object of the present invention is to provide a thermosetting resin composition that is compatible with electronic components in the next generation specifications and has good heat resistance and excellent storage stability.

As a result of earnest researches in the situation where the laminate sheet material has various characteristics as described above, the present inventors have found that an epoxy resin composition containing an epoxy resin and a resin having a specific skeleton structure is polyfunctional. It has been found that by including a phenol resin and an amine compound having physiological activity, a resin composition suitable for the above-mentioned purpose can be obtained, and the present invention has been completed.
That is, this invention provides the following thermosetting resin compositions.

1. A heat characterized by containing an epoxy resin (A), a resin (B) having a carbonate skeleton, a urethane skeleton and / or an imide skeleton, a polyfunctional phenol resin (C) and an amine compound (D) having a physiological activity. Curable resin composition.

（式中、複数個のＲはそれぞれ独立に炭素数１〜１８のアルキレン基、複数個のＸはそれぞれ独立に炭素数1〜１８のアルキレン基またはアリーレン基を示し、ｍおよびｎはそれぞれ独立に1〜２０の整数であり、Ｙは３価の有機基を示す。） 2. (B) The thermosetting resin composition according to 1 above, wherein the component is a modified polyamideimide resin having a structural unit represented by the following general formula (I).

(Wherein a plurality of R's are each independently an alkylene group having 1 to 18 carbon atoms, a plurality of X's are each independently an alkylene group having 1 to 18 carbon atoms or an arylene group, and m and n are each independently (It is an integer of 1 to 20, and Y represents a trivalent organic group.)

3. Component (C) is composed of novolak phenol resin, high ortho type novolak phenol resin, terpene modified phenol resin, terpene phenol modified phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, salicylaldehyde type phenol resin and benzaldehyde type phenol resin. 3. The thermosetting resin composition according to the above 1 or 2, which is at least one polyfunctional phenol resin selected from the group consisting of:
4). (D) Thermosetting composition in any one of said 1-3 whose component is hexamethylenetetramine.

  The thermosetting resin composition of the present invention can maintain heat resistance without deteriorating mechanical properties, has excellent storage stability, and is suitably used as an adhesive or protective film for electronic members and the like. can do.

The thermosetting resin composition of the present invention comprises an epoxy resin (A), a resin (B) having a carbonate skeleton, a urethane skeleton and / or an imide skeleton, a polyfunctional phenol resin (C), and an amine compound having a physiological activity ( D) is contained.
Hereinafter, the present invention will be described in detail.

  The epoxy resin of component (A) used in the present invention has an epoxy group in the molecule, and is a bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, Examples thereof include aliphatic chain epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, resins made of diglycidyl etherified products of biphenol, and diglycidyl etherified products of naphthalenediol. Two or more of these may be used in combination.

Examples of the resin having a carbonate skeleton, a urethane skeleton, and / or an imide skeleton as the component (B) include carbonate, urethane, imide, amideimide, and a resin having a plurality of these skeletons. Specific examples include polycarbonate, polyurethane, polyimide, polyamideimide and the like having the skeleton in the structural unit.
As the component (B), a modified polyamideimide resin having a structural unit represented by the following general formula (I) is particularly preferable.

（式中、複数個のＲはそれぞれ独立に炭素数１〜１８のアルキレン基、複数個のＸはそれぞれ独立に炭素数1〜１８のアルキレン基またはアリーレン基を示し、ｍおよびｎはそれぞれ独立に1〜２０の整数であり、Ｙは３価の有機基を示す。）

(Wherein a plurality of R's are each independently an alkylene group having 1 to 18 carbon atoms, a plurality of X's are each independently an alkylene group having 1 to 18 carbon atoms or an arylene group, and m and n are each independently (It is an integer of 1 to 20, and Y represents a trivalent organic group.)

The modified polyamideimide resin having the structural unit represented by the general formula (I) includes, for example, a trivalent or higher polycarboxylic acid having an acid anhydride group and a derivative thereof, and a diisocyanate represented by the following general formula (II) Can be obtained, for example, by reacting in the presence of a nitrogen-free polar solvent.
In the structure of the general formula (I), the polar groups of the urethane bond system are aggregated to form a microphase separation structure, and when an aromatic polyisocyanate is used, the cured product is affected by the rigidity and conjugation of the aromatic ring. Excellent heat resistance and flexibility can be achieved.

（式中、複数個のＲはそれぞれ独立に炭素数１〜１８のアルキレン基を、複数個のＸはそれぞれ独立に炭素数1〜１８のアルキレン基またはアリーレン基を示し、ｍおよびｎはそれぞれ独立に1〜２０の整数である。）
なお、（Ｂ）成分として、上記一般式（I）の構造単位以外の構造単位を有しても良く、例えば、前記３価のポリカルボン酸およびその誘導体以外の多価カルボン酸（ジカルボン酸、テトラカルボン酸二無水物を併用したり、前記一般式（II）で示される構造以外の構造を有するジイソシアネートを併用することで、そのような構造単位を持たせることができる。

(Wherein a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, a plurality of X's each independently represents an alkylene group or arylene group having 1 to 18 carbon atoms, and m and n are each independently 1 is an integer of 1 to 20.)
In addition, as (B) component, you may have structural units other than the structural unit of the said general formula (I), for example, polyvalent carboxylic acids other than the said trivalent polycarboxylic acid and its derivative (dicarboxylic acid, Such a structural unit can be provided by using tetracarboxylic dianhydride in combination or using a diisocyanate having a structure other than the structure represented by the general formula (II).

  The blending amount of the component (B) is preferably 300 to 5000 parts by mass and more preferably 1600 to 3500 parts by mass with respect to 100 parts by mass of the epoxy resin (A) from the viewpoint of viscoelasticity. (A) The effect of imparting elastic properties can be obtained by setting the component (B) to 300 parts by mass or more with respect to 100 parts by mass of the epoxy resin. The effect of suppressing embrittlement can be obtained.

  The (C) component polyfunctional phenolic resin is a polymer compound that usually functions as a curing agent component for the (A) epoxy resin and is mainly synthesized by reacting phenols with aldehydes. Selected from the group consisting of type novolac phenolic resin, terpene modified phenolic resin, terpene phenol modified phenolic resin, aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, salicylaldehyde type phenolic resin, and benzaldehyde type phenolic resin. It is preferable from the viewpoint.

(C) It is preferable that 1-100 mass% of at least 1 or more types of the polyfunctional phenol resin selected from said group is contained in a component, and it is more preferable that 1-80 mass% is contained. By setting the content to 1% by mass or more, a sufficient heat resistance effect can be obtained.
The component (C) is preferably contained in an amount of 10 to 1000 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin (A) from the viewpoint of mechanical strength, heat resistance and flexibility. preferable.

Examples of the amine compound having a physiologically active action as the component (D) include hexamethylenetetramine (hexamine, urotropine), epinephrine, propylhexedrine, amphetamine, mescaline, 2-phenylethanamine, and the like. Considering the properties, hexamethylenetetramine is most preferable.
(D) It is preferable to contain 0.1-50 mass parts from viewpoints of an active effect | action, stability, etc. with respect to 100 mass parts of (A) epoxy resins, and it is contained 0.5-10 mass parts. More preferred.

An inorganic filler can be added to the thermosetting resin composition of the present invention for the purpose of improving its handling, heat resistance, thermal conductivity, and thixotropy. There are no particular restrictions on the inorganic filler, such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum nitride, aluminum borate whisker, boron nitride, crystal Silica, amorphous silica, talc, layered double hydroxide and the like can be used.
As for the usage-amount of an inorganic filler, 1-25 volume parts is desirable with respect to 100 volume parts of (A)-(D) component of a thermosetting resin composition. When the amount is 1 part by volume or more, the heat resistance of the cured product does not become insufficient, and when the amount is 25 parts by volume or less, dispersibility does not decrease.

The thermosetting resin composition of the present invention can be produced by mixing and stirring the above components. The mixing method is not particularly limited, and examples thereof include a pulverizing and mixing method in which a solid is mixed using a roll crusher, a hammer mill, a roll mill, a ball mill, a jet mill, a vibration mill, and the like, and a method in which the solid is dissolved in a solvent and mixed. . The mixing temperature is preferably near room temperature in consideration of the reactivity of the resin.
An organic solvent can be used for mixing. There are no particular restrictions on the organic solvent, and in consideration of the volatility during curing and improvement in coating properties, methyl ethyl ketone, acetone, methanol, butyl cellosolve, dimethylformamide, N-methylpyrrolidone, cyclohexanone, diethylene glycol dimethyl ether, γ-butyrolactone, isobutane, etc. It is mentioned as preferable.
These organic solvents are preferably used so that the solid content of the thermosetting resin composition (that is, components other than the organic solvent) is 30 to 70% by mass.

  The thermosetting resin composition of the present invention includes a semiconductor chip, a SoC mounting substrate, a liquid encapsulant, a wiring board, a build-up board, a flexible wiring board, a liquid crystal panel substrate, a polarizing plate, an in-vehicle power module substrate, a SiC substrate, and the like. It is useful as an adhesive for an electronic member and a material for forming a protective film. In particular, it is suitable for overcoat materials for electronic parts, interlayer insulating films, surface protective films, and solder resist films.

  EXAMPLES Next, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples. In addition, the resin composition obtained by each Example and the comparative example measured and evaluated the physical property with the following method.

(1) Gel time Using a gel timer (manufactured by Nippon Fenol Co., Ltd., gelation tester) according to JIS C2161, the time until the sample was stirred on a hot plate at 120 ° C. and lost its fluidity was measured.

(2) Tensile strength and elongation at break The sample was coated on a polyethylene terephthalate film with a coating thickness of 0.04 mm and heated on a 120 ° C. hot plate for 10 minutes to volatilize the solvent γ-butyrolactone to a thickness of 0.020 mm. A film was obtained. The sample was cut into a width of 10 mm, a thickness of 0.040 mm, and a length of 150 mm to obtain a test piece.
The measurement was performed according to JIS K7127 using an autograph (manufactured by Shimadzu Corporation, IM-100 type), applying a tensile load at a fulcrum distance of 50 mm and a tensile speed of 100 mm / min, and the maximum strength until break [N], And the elongation at break was measured. Tensile strength [MPa] is calculated by maximum strength / (test specimen thickness × width), and elongation at break [%] is calculated by [(distance between fulcrums at break−distance between fulcrums) / distance between fulcrums] × 100. did.

(3) Weight reduction rate during heating The sample was weighed in an aluminum pan and heated on a hot plate at 250 ° C. for 1 hour. The weight before and after the test was measured, and the reduction rate [%] was calculated by [(weight before test−weight after test) / weight before test] × 100.

(4) Storage stability The sample was put into a glass storage bottle, heated in a dryer at 100 ° C. for 12 hours, and the viscosity before and after heating was measured. Viscosity was measured using an R-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-80U type, rotor 3 ° × R9.7) at a rotation speed of 10 rpm and a measurement temperature of 25 ° C.

Production Example 1: Production of polyamideimide resin varnish (PAI-1) A 3-methyl-1,5-pentanediol-based polycarbonate was added to a 1-liter four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer. 200 g of resin [manufactured by Daicel Chemical Industries, Ltd., trade name: PLACCCEL CD-220PL], 50 g of 4,4′-diphenylmethane diisocyanate and 167 g of γ-butyrolactone were charged and reacted at 140 ° C. for 5 hours. Thereafter, 58 g of trimellitic anhydride, 25 g of 4,4′-diphenylmethane diisocyanate, and 272 g of γ-butyrolactone were charged and reacted at 160 ° C. for 6 hours to obtain a polyamideimide resin varnish having a structural unit represented by the above general formula (I) ( PAI-1) was obtained.

Production Example 2: Production of Aralkyl-Modified Polyamideimide Resin Varnish (PAI-2) Into a 1 liter four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer, 3-methyl-1,5- 200 g of pentanediol-based polycarbonate resin [manufactured by Daicel Chemical Industries, Ltd., trade name: PLACCCEL CD-220PL], 50 g of 4,4′-diphenylmethane diisocyanate and 167 g of γ-butyrolactone were charged and reacted at 150 ° C. for 3 hours. Thereafter, 38 g of trimellitic anhydride, terpene-bisphenol copolymer (trade name, YS Polystar K125, molecular weight 650, softening point 125 ° C.) 20 g, 25 g of 4,4′-diphenylmethane diisocyanate and γ-butyrolactone 272 g was charged and reacted at 160 ° C. for 6 hours to obtain an aralkyl-modified polyamideimide resin varnish (PAI-2) having a structural unit represented by the general formula (I).

Example 1
(A) component is bisphenol A type glycidyl ether type epoxy resin [manufactured by Tohto Kasei Co., Ltd., YD-8125, epoxy equivalent 175], 3 parts by mass, (B) component is polyamideimide resin (PAI -1) Resin content 79 parts by mass, (C) component terpene-bisphenol copolymer [manufactured by Yashara Chemical Co., Ltd., trade name: YS Polystar K125, molecular weight 650, softening point 125 ° C.] 20 parts by mass, component (D) Hexamethylenetetramine: 1 part by mass, 100 g of γ-butyrolactone was added to the solvent, and mixed by stirring to obtain a sample of a thermosetting resin composition. Table 1 shows the measurement and evaluation results of the physical properties.

Example 2
The same procedure as in Example 1 was performed except that caffeine (1 part by mass) was used as the component (D). Table 1 shows the measurement and evaluation results of the physical properties.

Example 3
The same procedure as in Example 1 was performed except that 1 part by mass of propylhexedrine was used as the component (D). Table 1 shows the measurement and evaluation results of the physical properties.

Comparative Example 1
(A) component is bisphenol A type glycidyl ether type epoxy resin [manufactured by Tohto Kasei Co., Ltd., YD-8125, epoxy equivalent 175], 3 parts by mass, (B) component is polyamideimide resin (PAI -1) Resin content 80 parts by mass, (C) component terpene-bisphenol copolymer [manufactured by Yashara Chemical Co., Ltd., trade name: YS Polyster K125, molecular weight 650, softening point 125 ° C.] 20 parts by mass, component (D) As an alternative, 0.5 parts by mass of a block carboxylic acid [manufactured by NOF Corporation, trade name: Lcat-1] and a block carboxylic acid accelerator [manufactured by NOF Corporation, trade name: HK-6] 5 parts by mass of 100 g of γ-butyrolactone was added to the solvent and mixed by stirring to obtain a sample of a thermosetting resin composition. Table 1 shows the measurement and evaluation results of the physical properties.

Comparative Example 2
(A) component is bisphenol A type glycidyl ether type epoxy resin [manufactured by Tohto Kasei Co., Ltd., YD-8125, epoxy equivalent 175], 3 parts by mass, (B) component is polyamideimide resin (PAI -1) Resin content 80 parts by mass, (C) component terpene-phenol copolymer [manufactured by Yashara Chemical Co., Ltd., trade name: Mighty Ace G150, molecular weight 700, softening point 150 ° C.] 20 parts by mass, component (D) As an alternative, 0.5 parts by mass of a block carboxylic acid [manufactured by NOF Corporation, trade name: Lcat-1] and a block carboxylic acid accelerator [manufactured by NOF Corporation, trade name: HK-6] 5 parts by mass of 100 g of γ-butyrolactone was added to the solvent and mixed by stirring to obtain a sample of a thermosetting resin composition. Table 1 shows the measurement and evaluation results of the physical properties.

Comparative Example 3
(A) component is bisphenol A type glycidyl ether type epoxy resin [manufactured by Tohto Kasei Co., Ltd., YD-8125, epoxy equivalent 175] 3 parts by mass, (B) component is polyamideimide resin varnish obtained in Production Example 2 ( PAI-2) 80 parts by mass of a resin, 100 g of γ-butyrolactone was added to a solvent, and the mixture was stirred and mixed to obtain a sample of a thermosetting resin composition. Table 1 shows the measurement and evaluation results of the physical properties.

Comparative Example 4
(A) component is bisphenol A type glycidyl ether type epoxy resin [manufactured by Tohto Kasei Co., Ltd., YD-8125, epoxy equivalent 175], 3 parts by mass, (B) component is polyamideimide resin (PAI -1) 100 parts by mass of resin, 100 g of γ-butyrolactone was added to the solvent, and the mixture was stirred and mixed to obtain a sample of a thermosetting resin composition. Table 1 shows the measurement and evaluation results of the physical properties.

Comparative Example 5
(A) component is bisphenol A type glycidyl ether type epoxy resin [manufactured by Tohto Kasei Co., Ltd., YD-8125, epoxy equivalent 175], 3 parts by mass, (B) component is polyamideimide resin (PAI -1) Resin content 100 parts by mass, (D) As an alternative to component, block carboxylic acid [manufactured by NOF Corporation, trade name: Lcat-1] 0.5 part by mass and block carboxylic acid accelerator [NOF ( Co., Ltd., trade name: HK-6] 0.5 parts by mass, 100 g of γ-butyrolactone was added to the solvent, and mixed by stirring to obtain a sample of a thermosetting resin composition. Table 1 shows the measurement and evaluation results of the physical properties.

  From Table 1, the thermosetting resin composition of the present invention contains gel components and tensile properties equivalent to those of Comparative Examples 1 to 5 that do not contain the C component and / or the D component by containing all of the A to D components. However, it can be seen that it exhibits particularly excellent storage stability.

  The thermosetting resin composition of the present invention can maintain heat resistance without deteriorating curability and mechanical properties as described above, has excellent storage stability, and can be used for adhesives such as electronic members. It can be suitably used as a protective film.

Claims (4)

  A heat characterized by containing an epoxy resin (A), a resin (B) having a carbonate skeleton, a urethane skeleton and / or an imide skeleton, a polyfunctional phenol resin (C) and an amine compound (D) having a physiological activity. Curable resin composition. The thermosetting resin composition according to claim 1, wherein the component (B) is a modified polyamideimide resin having a structural unit represented by the following general formula (I).

(Wherein a plurality of R's are each independently an alkylene group having 1 to 18 carbon atoms, a plurality of X's are each independently an alkylene group having 1 to 18 carbon atoms or an arylene group, and m and n are each independently (It is an integer of 1 to 20, and Y represents a trivalent organic group.)   Component (C) is a novolak phenol resin, a high ortho type novolak phenol resin, a terpene modified phenol resin, a terpene phenol modified phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a salicylaldehyde type phenol resin, or a benzaldehyde type phenol resin. The thermosetting resin composition according to claim 1 or 2, which is at least one polyfunctional phenol resin selected from the group consisting of:   (D) Thermosetting composition in any one of said 1-3 whose component is hexamethylenetetramine.