KR20120112388A - Polyamide compound and epoxy resin composition containing same - Google Patents

Abstract

The present invention has a polyamide compound having a partial structure represented by the following general formula (I) and / or general formula (I ′) in a repeating unit, wherein X in the formula represents a hydrogen atom or a hydroxyl group. And an epoxy resin composition using the compound as a curing agent. The polyamide compound of this invention can provide high peel strength with respect to the surface with small surface roughness with respect to an epoxy resin, without increasing the compounding quantity of a filler.

Description

Polyamide compound and epoxy resin composition containing it {POLYAMIDE COMPOUND AND EPOXY RESIN COMPOSITION CONTAINING SAME}

The present invention relates to a novel polyamide compound and an epoxy resin composition containing the same, and in particular, a novel polyamide compound having a specific structure in a repeating unit, and an epoxy suitable for a build-up insulating material containing the same. It relates to a resin composition.

Epoxy resins are excellent in insulation, dimensional accuracy, and strength, and thus are commonly used in printed wiring boards. In particular, epoxy resins have excellent properties such as high glass transition temperature, low coefficient of linear expansion, flexibility, and the like. And using the polyamide compound which has a phenolic hydroxyl group for a hardening | curing agent is proposed (patent document 1).

On the other hand, in developing a miniaturized printed board, since the surface roughness of the printed board tends to be small, in recent years, a thermosetting insulating resin capable of maintaining high peel strength with respect to a surface having a small surface roughness is It is required. In addition, in order to increase the peel strength, there is a means for adding a filler to the resin to lower the linear expandability. However, when the amount of the filler is increased, a problem arises in that the tensile strength of the resin decreases. Therefore, although the linear expandability must be reduced without increasing the amount of the filler to be blended, such a material has not yet been found.

Patent Document 1: International Publication No. 2006/129480

Therefore, the 1st objective of this invention is providing the hardening | curing agent which can provide high peeling strength with respect to the surface with small surface roughness with respect to an epoxy resin, without increasing the compounding quantity of a filler.

The 2nd object of this invention is to provide the epoxy resin composition with high peeling strength with respect to the surface with small surface roughness.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve said various objectives, the present inventors discovered the novel polyamide compound which functions as a hardening | curing agent which can provide high peel strength with respect to the surface with small surface roughness with respect to an epoxy resin. The present invention has been reached by discovering.

That is, this invention has the partial structure represented by the following general formula (I) and / or general formula (I ') in a repeating unit, The polyamide compound characterized by the above-mentioned, and the epoxy resin containing this polyamide compound Composition.

However, X in the said general formula represents a hydrogen atom or a hydroxyl group.

In addition to the partial structure which has the said sulfone bond, the polyamide compound of this invention may have the partial structure represented by the following general formula (II) further in the said repeating unit.

Moreover, the polyamide compound of this invention may have the partial structure represented by the following general formula (II ') in addition to the partial structure which has the said sulfone bond in the said repeating unit.

The polyamide compound of the present invention is particularly a polyamide compound composed of a diamine compound and a dicarboxylic acid compound, wherein the diamine compound is only 3,3'-diaminodiphenylsulfone or 3,3'-diamino. It is preferred to consist only of diphenylsulfone and 2,4-diaminophenol.

The epoxy resin composition of this invention needs to contain 1-100 weight part of polyamide compounds of this invention with respect to 100 weight part of epoxy resins, As a filler, spherical silica whose average particle diameter is 0.01-20 micrometers, and / or It is preferable to further contain a phosphorus flame retardant. Moreover, it is preferable that the usage-amount of the said phosphorus flame retardant is 5-100 weight part with respect to a total of 100 weight part of an epoxy resin and a polyamide compound.

By using the polyamide compound of this invention as a hardening | curing agent of an epoxy resin, the thermosetting epoxy resin composition which has high peeling strength with respect to the surface which has small surface roughness, and is suitable as a buildup type insulating resin material is obtained.

The polyamide compound of this invention is a polyamide compound obtained by reaction with the diamine compound which has 3,3'- diamino diphenyl sulfone as a main component, and a dicarboxylic acid compound, and is a non-document compound. In this invention, various diamine compounds can be used together with the said 3,3'- diamino diphenyl sulfone.

As a diamine compound which can be used with the said 3,3'- diamino diphenyl sulfone, m-phenylenediamine, p-phenylenediamine, m-tolylenediamine; 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylthio Ether, 4,4'-diaminodiphenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenyl Thioether, 3,3'-dimethoxy-4,4'-diaminodiphenylthioether;

4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone; 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane; 2,2'-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane; Betidine, 3,3'-dimethylbentidine, 3,3'-dimethoxybentidine; 3,3'-diaminodiphenyl; p-xylylenediamine, m-xylylenediamine, o-xylylenediamine; 2,2'-bis (4-aminophenoxyphenyl) propane, 1,3-bis (4-aminophenoxyphenyl) benzene, 1,3'-bis (3-aminophenoxyphenyl) propane; Bis (4-amino-3-methylphenyl) methane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3-ethylphenyl) methane, bis (4-amino-3,5- Diethylphenyl) methane, bis (4-amino-3-propylphenyl) methane, bis (4-amino-3,5-dipropylphenyl) methane; 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane; 2, 4- diamino phenol, etc. are mentioned.

In the present invention, it is particularly preferable to use 3,3'-diaminodiphenylsulfone alone or to use 3,3'-diaminodiphenylsulfone and 2,4-diaminophenol in combination. By doing in this way, since the reactivity with various epoxy resins improves, the resin composition with a higher resin strength can be obtained.

As the dicarboxylic acid compound used in the present invention, for example, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-oxy ibenzoic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-methylene Ibenzoic acid, 4,4'-thio ibenzoic acid, 3,3'-carbonyl ibenzoic acid, 4,4-sulfonyl ibenzoic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid , 2,6-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid, 3-hydroxyisophthalic acid, 2 2, 2'-bis (3-carboxyphenyl) hexafluoro propane, 2, 2'-bis (4-carboxyphenyl) hexafluoro propane, etc. are mentioned. From the viewpoint of imparting proper thermal stability and solubility to the polyamide compound of the present invention, it is particularly preferable to use isophthalic acid and / or terephthalic acid.

Although the polyamide compound of this invention is illustrated concretely below, this invention is not limited by these specific examples.

The polyamide compound of the present invention is useful as a curing agent for epoxy resins and has a small surface roughness by containing 1 to 100 parts by weight of the polyamide compound of the present invention, preferably 5 to 80 parts by weight, based on 100 parts by weight of the epoxy resin. The thermosetting epoxy resin composition which has a high peeling strength with respect to the surface which has a can be obtained.

The epoxy resin used for the epoxy resin composition of this invention is not restrict | limited, It can select suitably from a well-known aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, etc., and can use. As an aromatic epoxy compound, hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4'- dihydroxy biphenyl, a novolak, tetrabromobisphenol A, 2, 2-bis (4- And glycidyl ether compounds of polyhydric phenols such as hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

As the alicyclic epoxy compound, a cyclohexene oxide or a cyclopentene oxide-containing compound obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent Can be mentioned. For example, hydrogenated bisphenol A diglycidyl ether; 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl- 3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxyl Latex, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate; Bis (3,4-epoxycyclohexylmethyl) adipate, methylenebis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide, Ethylene bis (3, 4- epoxycyclohexane carboxylate), dioctyl epoxy hexahydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, etc. are mentioned.

As an aliphatic epoxy compound, it synthesize | combined by the vinyl polymerization of the polyglycidyl ether of an aliphatic polyhydric alcohol or its alkylene oxide adduct, the polyglycidyl ester, glycidyl acrylate, or glycidyl methacrylate of an aliphatic long-chain polybasic acid. Homopolymers; And copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate with other vinyl monomers.

Representative compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, and tetraglycidyl ether of sorbitol Glycidyl ethers of polyhydric alcohols such as hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol; Polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin; And diglycidyl esters of aliphatic long-chain dibasic acids. Moreover, the monoglycidyl ether of the aliphatic higher alcohol, the monoglycidyl ether of polyphenol alcohol obtained by adding alkylene oxide to phenol, cresol, butyl phenol, and these; Glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized polybutadiene, and the like.

In addition to the polyamide compound of this invention, another epoxy resin hardening | curing agent can also be used for the epoxy resin composition of this invention. Thus, by using it in combination with another hardening | curing agent, the viscosity, hardening characteristic, physical property after hardening, etc. of the curable composition obtained can be controlled. As said other hardening | curing agent used with the polyamide compound of this invention, a well-known latent hardening | curing agent, a polyamine compound, a polyphenol compound, etc. are mentioned.

Examples of the latent curing agent include dicyandiamide, hydrazide, imidazole compounds, amine adducts, ketimines, tertiary amines, and the like. By using these latent hardeners, since the one-component curable composition which is easy to handle can be obtained, using the said latent hardener together is a preferable aspect of this invention.

As said polyamine compound, For example, Aliphatic polyamine, such as ethylenediamine, diethylene triamine, and triethylene tetramine; Mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxa Alicyclic polyamines such as spiro [5,5] undecane; aliphatic amines having an aromatic ring such as m-xylylene diamine; m-phenylenediamine, 2,2-bis (4-aminophenyl) propane, diaminodiphenylmethane, diaminodiphenylsulfone, α, α-bis (4-aminophenyl) -p-diisopropylbenzene, And aromatic polyamines such as 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane.

As said polyphenol compound, For example, a phenol novolak, o-cresol novolak, t-butylphenol novolak, dicyclopentadicresol, terpendiphenol, terpendicatechol, 1,1,3-tris (3 Tert-butyl-4-hydroxy-6-methylphenyl) butane, butylidenebis (3-tert-butyl-4-hydroxy-6-methylphenyl), 2,2-bis (4-hydroxyphenyl)- 1,1,1,3,3,3-hexafluoropropane etc. are mentioned. In particular, the phenol novolak is preferable because the electrical properties and mechanical strength of the epoxy resin obtained are suitable for use for laminates.

Flame retardants, such as a phosphorus flame retardant, can be mix | blended with the epoxy resin composition of this invention. It is preferable that the compounding quantity of the flame retardant is 5-100 weight part with respect to a total of 100 weight part of the compounding quantity of an epoxy resin and a hardening | curing agent. In this invention, it is especially preferable to use the phosphate amide compound represented by the following general formula (III).

However, R ¹ , R ² and R ³ in the above formulas each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, or a halogen atom, and Z ¹ and Z ² are a direct bond, Or an alkylene group or an alkylidene group having 1 to 4 carbon atoms, and ring C represents an arylene group, a cycloalkylene group or an arylene-alkylene (alkylidene) -allyylene group having 6 to 18 carbon atoms. .

Although the epoxy resin composition of this invention is excellent in the physical properties (high glass transition temperature, low linear expansion coefficient, tensile strength, elongation, flexibility, etc.) of the hardened | cured material, even without using a filler, Furthermore, the filler (filler) which uses It is preferable. As a filler in this case, it is preferable to use fibrous fillers, such as glass fiber, aluminum borate whisker, boron nitride whisker, potassium titanate whisker, titanium oxide whisker, and spherical fillers, such as a silica, fused silica, and alumina.

In particular, it is preferable to use spherical silica or spherical fused silica in terms of the physical properties of the cured product as a filler. However, silica, alumina, aluminate borosilicate, alumina nitride, boron nitride, potassium titanate, titanium oxide, and the like, which are not limited to fibrous or spherical forms, may also be used, as well as talc, mica, calcium carbonate, glass chips, and glass beads. Glass balloons, calcium silicates, aluminum hydroxide, barium sulfate, magnesia, ferrite, various metal fine particles, graphite, carbon, and the like; Inorganic fibers such as carbon fiber, glass fiber, boron fiber, silicon carbide fiber, alumina fiber and silica alumina fiber; Organic fibers, such as aramid fiber, polyester fiber, cellulose fiber, and carbon fiber, can also be used.

When using a fibrous filler, it is preferable to select length and aspect ratio of a major axis direction suitably according to a use. In the case of a spherical filler, it is preferable that a particle size is small in spherical form, and it is especially preferable to use the thing of the range whose average particle diameter is 0.01-20 micrometers.

Another additive can be added to the epoxy resin composition of this invention as needed. Plasticizers such as natural waxes, synthetic waxes, and metal salts of long-chain aliphatic acids; Mold release agents such as acid amides, esters, paraffins; Stress relieving agents such as nitrile rubber and butadiene rubber; Inorganic flame retardants such as antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, calcium aluminate; Brominated flame retardants, such as tetrabromobisphenol A, tetrabromo phthalic anhydride, hexabromobenzene, and brominated phenol novolak; Phosphorus flame retardants other than the phosphorus flame retardants described above; Coupling agents such as a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent; Coloring agents such as dyes and pigments; Oxidation stabilizers, light stabilizers, moisture resistance enhancers, thixotropic imparting agents, diluents, antifoaming agents, various other resins, tackifiers, antistatic agents, lubricants, ultraviolet absorbers, or alcohols, ethers, acetals, ketones, esters Organic solvents such as alcohols, alcohol esters, ketone alcohols, ether alcohols, ketone ethers, ketone esters, ester ethers, and aromatic solvents.

The epoxy resin composition of this invention is suitable for use as an electrical / electronic material insulating resin, such as a multilayer printed wiring board, a semiconductor interposer, a semiconductor passivation film, or use for the use of heat-resistant composite materials for aerospace.

Example

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Polyamide Compound Having Structure of PA-1

39.7 g (0.16 mol) of 3,3'- diamino diphenyl sulfone was dissolved in 160 g of N-methylpyrrolidone (hereinafter referred to as NMP) and 30.3 g of pyridine. 32.5 g (0.16 mol) of isophthaloyl chloride was dissolved in 64 g of NMP, and added dropwise to the solution at a temperature of -15 to 0 ° C.

The reaction was carried out for 2 hours while maintaining the temperature at -15 to 0 ° C, and the reaction was carried out at room temperature for 2 hours. After reprecipitation with about 2 liters of ion-exchanged water, it filtered, and it dried under reduced pressure at 150 degreeC for 3 hours, and obtained 50g (yield 83%) of white powders (form polymer PA-1). From the infrared absorption spectrum, it was confirmed that the obtained compound had an amide bond, and gel permeation chromatography confirmed that the weight average molecular weight was 11800 polymer. Moreover, the viscosity was 430 mPas (30 weight% NMP solution) as a result of the measurement by the E-type clay meter at 25 degreeC.

Synthesis Example 2-4

In the same manner as in Synthesis example 1, the following polyamide compounds PA-2 to 4 were synthesized. The weight average molecular weight and viscosity of the obtained polyamide compound were as follows.

PA-2:

Weight average molecular weight: 5970,

Viscosity: 200 mPas (25 ° C., 30 wt% NMP solution)

PA-3:

Weight average molecular weight: 13540,

Viscosity: 525 mPas (25 ° C, 30 wt% NMP solution)

PA-4:

Weight average molecular weight: 50370,

Viscosity: 2500 mPas (25 ° C, 30 wt% NMP solution)

Examples 1-4

The epoxy resin composition shown in Table 1 was prepared using polyamide compound PA-1-PA-4. The compounding amount is a weight ratio.

On the PET sheet, the epoxy resin composition containing polyamide was apply | coated so that it might become thickness of 40 micrometers, and the thin film resin dried for 10 minutes at 100 degreeC was vacuum-heat-laminated at 100 degreeC on the glass epoxy board | substrate. Furthermore, after hardening at 180 degreeC for 1 hour and making a surface clean, plating was performed and the adhesive strength measurement test piece was obtained and the following measurement was performed.

(1) Based on JIS-C6481, the peeling strength of the film was examined by the 90 degree peeling test of a 1 cm width pattern.

(2) Based on JIS-BO601, the surface roughness was measured using VK-9710 made from Keyence Co., Ltd.

(3) Based on JIS-K7197, the linear expansion coefficient was measured using TMA / SS6100 by SAI NANO TECHNOLOGY CO., LTD.

Comparative Examples 1-7

The epoxy resin composition of Table 2 was prepared. The compounding amount is a weight ratio.

[Table 1]

[Table 2]

Said HPA-1-HPA-7 is a compound shown below.

As apparent from Table 1 and Table 2, when the epoxy resin composition of the present invention was cured, it was confirmed to have high peel strength even on a surface with low roughness.

In particular, from the results of Comparative Example 1, even if a polyamide compound using diaminodiphenylsulfone having an amino group at the 4th position is used as a curing agent, the polyamide compound of the present invention using diaminodiphenylsulfone having an amino group at the 3rd position is used. It was confirmed that high peel strength, such as when used as a curing agent, was not obtained.

By using the polyamide compound of this invention as a hardening | curing agent of an epoxy resin, the thermosetting epoxy resin composition which has high peeling strength with respect to the surface which has small surface roughness is obtained, and this epoxy resin composition is suitable as a buildup type insulation resin material. It can be used in electrical and electronic material insulating resins such as multilayer printed wiring boards, semiconductor interposers, semiconductor passivation films, and heat-resistant composite materials for aerospace.

Claims (10)

Polyamide compound characterized by having a partial structure represented by the following general formula (I) and / or general formula (I ') in a repeating unit;

Provided that X in the above formula represents a hydrogen atom or a hydroxyl group. The method of claim 1,
Polyamide compound which has a partial structure further represented by the following general formula (II) and / or following general formula (II ') in a repeating unit;

The method of claim 1,
A polyamide compound, wherein the polyamide compound is a polyamide compound obtained by reacting a 3,3'-diaminodiphenylsulfone with a dicarboxylic acid compound. The method of claim 1,
The polyamide compound whose said polyamide compound is a polyamide compound formed by making 3,3'- diamino diphenyl sulfone, 2, 4- diamino phenol, and a dicarboxylic acid compound react. It is made to contain 1-100 weight part of polyamide compounds in any one of Claims 1-4 with respect to 100 weight part of epoxy resins, The epoxy resin composition characterized by the above-mentioned. The method of claim 5,
Moreover, the epoxy resin composition formed by containing a filler. The method according to claim 6,
The epoxy resin composition whose said filler is spherical silica of 0.01-20 micrometers in average particle diameter. The method of claim 5,
The epoxy resin composition which mix | blends 5-100 weight part of phosphorus flame retardants with respect to a total of 100 weight part of an epoxy resin and a polyamide compound. 9. The method of claim 8,
Epoxy resin composition whose said phosphorus flame retardant is a phosphate amide compound represented with the following general formula (III);

Provided that R ¹ , R ² and R ³ in the above formulas each independently represent a hydrogen atom or an alkyl group, a cycloalkyl group or a halogen atom having 1 to 8 carbon atoms, and Z ₁ and Z ₂ are direct bonds, or An alkylene group or an alkylidene group having 1 to 4 carbon atoms is represented, and ring C represents an arylene group, a cycloalkylene group or an arylene-alkylene (alkylidene) -arylene group having 6 to 18 carbon atoms. . 9. The method of claim 8,
Moreover, the epoxy resin composition formed by containing a filler.