JP5125579B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition.

  In recent years, polyimide films have come to be used in many electronic devices and the like, and the application range has been expanded. On the other hand, an adhesive mainly composed of an epoxy resin is used in electronic devices and the like for reasons such as excellent reliability and adhesiveness in a high temperature / high humidity environment.

  Further, in order to impart toughness to the epoxy resin composition, a core-shell comprising a core composed of a styrene-butadiene copolymer and the like, and a shell composed of a methyl methacrylate copolymer covering the core, etc. Methods of adding mold rubber particles are known.

However, the conventional epoxy resin adhesive composition has insufficient adhesiveness to polyimide, and there is a problem that the adhesiveness is lowered particularly when left in a high temperature / high humidity environment for a long time. In addition, since the conventional epoxy resin adhesive composition has a high curing temperature and has little influence on the polyimide film, it takes several minutes to several tens of minutes to cure at a relatively low temperature (for example, 160 ° C.). Not suitable for bonding.
Further, when core-shell type rubber particles are added, the adhesion to polyimide is somewhat improved, but there is room for further improvement in adhesion. In electronic circuits, etc., the width of the bonding surface may be about several μm, but the resin composition using core-shell type rubber particles is applied to a location where the bonding surface is about several μm. There is a problem that the adhesiveness is lowered.

  Therefore, an object of the present invention is to provide a curable resin composition that can be cured at a low temperature and in a short time and that is excellent in adhesion to polyimide and moisture and heat resistance.

  The inventor of the present invention comprises an epoxy resin (A), a styrene-butadiene-methyl methacrylate terpolymer (B), a polyester urethane having an acid value of 5 KOHmg / g or less, a polyether ester amide, and a polyester amide. A curable resin composition containing at least one polymer (C) selected from can be cured at a low temperature and in a short time, and further becomes a curable resin composition having excellent adhesion to polyimide and heat and moisture resistance. As a result, the present invention has been completed.

That is, the following (1 ) is provided.
(1) Selected from the group consisting of epoxy resin (A), styrene-butadiene-methyl methacrylate terpolymer (B), polyester urethane having an acid value of 5 KOHmg / g or less, polyether ester amide, and polyester amide The styrene-butadiene-methyl methacrylate terpolymer (B) is contained in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin (A). 65 parts by mass, the content of the polyester urethane is 1 to 65 parts by mass with respect to 100 parts by mass of the epoxy resin (A), and the content of the polyetheresteramide and / or the polyesteramide is the above It is 1-65 mass parts with respect to 100 mass parts of epoxy resins (A), and an acid value is more than 5 KOHmg / g. Does not contain a polyester urethane, further contain a curing agent, the curing agent is a latent curing agent, curable resin composition.

  The curable resin composition of the present invention can be cured at a low temperature and in a short time, and is excellent in adhesion to polyimide and heat and humidity resistance.

Hereinafter, the present invention will be described in more detail.
The curable resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) has an epoxy resin (A), a styrene-butadiene-methyl methacrylate terpolymer (B), and an acid value of 5 KOHmg. It is a curable resin composition containing at least one polymer (C) selected from the group consisting of polyester urethane, polyether ester amide, and polyester amide that is / g or less.

  The epoxy resin (A) is not particularly limited as long as it is a compound having two or more epoxy groups. For example, bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexafluoroacetone, tetramethylbisphenol F Glycidyl ether type obtained by the reaction of polychlorophenol such as bixylenol and dihydroxynaphthalene with epichlorohydrin; fats such as glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol Reaction of aromatic polyhydric alcohols with epichlorohydrin Polyglycidyl ether type obtained by glycidyl ether ester type obtained by reaction of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid with epichlorohydrin; phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetra Polyglycidyl ester type derived from polycarboxylic acid such as hydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acid; from aminophenol, aminoalkylphenol, etc. Derived glycidylaminoglycidyl ether type; Glycidylaminoglycidyl ester type derived from aminobenzoic acid; Aniline, Toluidine, Tribromoaniline, Xylylenediamine, Diamy Glycidylamine type derived from nocyclohexane, bisaminomethylcyclohexane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, etc .; epoxidized polyolefin, glycidylhydantoin, glycidylalkylhydantoin, triglycidylcyanurate, etc. Can be mentioned. These may be used alone or in combination of two or more.

  The epoxy resin (A) preferably has at least one aromatic ring from the viewpoint of excellent mechanical strength and wet heat resistance of the cured product. In particular, bisphenol A-type epoxy resins and bisphenol F-type epoxy resins are preferable because they are easily available and have a good balance of physical properties of the cured product.

Next, the styrene-butadiene-methyl methacrylate terpolymer (B) (hereinafter referred to as “ternary copolymer (B)”) will be described.
The ternary copolymer (B) is a block copolymer composed of a block derived from styrene, a block derived from butadiene, and a block derived from methyl methacrylate. That is, a structure composed of a repeating unit represented by the following formula (S), a structure composed of a repeating unit represented by the following formula (B), and a structure composed of a repeating unit represented by the following formula (M). It is a block copolymer having.

As the ternary copolymer (B), a block copolymer having a structure represented by-(S) _n- (B) _m- (M) _1- (referred to as SBM structure),-(M) _o- (B) A block copolymer having a structure represented by _p- (S) _q- (referred to as MBS structure) may be mentioned, and these may be used alone or in combination.
The above S, B and M represent repeating units represented by the above formulas S, B and M, respectively. n, m, l, o, p and q each independently represent an integer of 10 to 1000.

  The weight average molecular weight of the terpolymer (B) is preferably 5,000 to 50,000, more preferably 5,000 to 30,000, and more preferably 10,000 to 20,000 from the viewpoint of excellent adhesion to polyimide and wet heat resistance. Is more preferable.

The manufacturing method of a ternary copolymer (B) is not specifically limited, A ternary copolymer (B) can be manufactured with a well-known polymerization method. For example, it can be obtained by mixing styrene, butadiene, methyl methacrylate and a polymerization initiator and polymerizing them by irradiating with ultraviolet rays.
Specific examples of the polymerization method of the ternary copolymer (B) include WO96 / 24620, US Pat. No. 6,255,448, WO2000 / 071501, and European Patent Application No. 1429913. And European Patent Application Publication No. 1178955 specification, International Publication No. 2000/049027 pamphlet and the like.

  Although content of a ternary copolymer (B) is not specifically limited, It is preferable that it is 1-65 mass parts with respect to 100 mass parts of epoxy resins (A), and it is 5-60 mass parts. More preferably, it is 10-50 mass parts. When the content of the ternary copolymer (B) is within this range, it can be cured at a low temperature and in a short time, and it is excellent in adhesion to polyimide and heat and moisture resistance.

Conventionally, core-shell type rubber particles used for imparting toughness have a problem in dispersibility. Further, the core-shell type rubber particles usually have a particle size of several μm, and it is difficult to form an extremely small adhesive layer of about several μm.
On the other hand, since the terpolymer (B) usually has a molecular size of about several nanometers to several tens of nanometers, the composition of the present invention has excellent fluidity and good film forming properties. Thus, even when applied to a location where the state of the adhesive interface is good and the width of the adhesive surface is about several μm, the adhesiveness to polyimide is excellent.

Hereinafter, the polymer (C) will be described.
The polymer (C) used in the composition of the present invention is at least one polymer selected from the group consisting of polyester urethane, polyether ester amide and polyester amide having an acid value of 5 KOH mg / g or less.
Since the composition of the present invention is superior in adhesion to polyimide film and heat-and-moisture resistance, as a polymer (C), a polyester urethane having an acid value of 5 KOHmg / g or less, a polyetheresteramide and / or a polyesteramide It is preferable to contain.

  The polyester urethane used in the composition of the present invention is a polymer having an ester bond and a urethane bond in the main chain. As said polyester urethane, the polymer obtained by making a polyester polyol and a polyisocyanate compound react is mentioned suitably from the point that an acid value becomes low, for example.

As said polyester urethane, what contains an aromatic dicarboxylic acid residue is preferable from the point which is excellent in the adhesiveness with respect to a polyimide. In particular, those containing a terephthalic acid residue are more preferred because of their superior adhesion to polyimide.
Moreover, as said polyester urethane, what contains a dimethylol butanoic acid residue and / or a dimethylol propionic acid residue is preferable from the point which is excellent in the adhesiveness with respect to a polyimide.
In addition, in this specification, an aromatic dicarboxylic acid residue means the structure remove | excluding the carboxy group from aromatic dicarboxylic acid. A dimethylol butanoic acid residue means a structure obtained by removing a carboxy group and a hydroxy group from dimethylol butanoic acid. The dimethylolpropionic acid residue means a structure obtained by removing a carboxy group and a hydroxy group from dimethylolpropionic acid.
An aromatic dicarboxylic acid refers to a compound having an aromatic ring and two carboxy groups bonded to the aromatic ring.

As said polyester polyol, the compound which has a 2 or more hydroxy group obtained by reaction of aromatic dicarboxylic acid and a polyol compound is mentioned suitably, for example. Moreover, the compound which has a 2 or more hydroxy group obtained by reaction of a dimethylol butanoic acid and a polyol compound is also mentioned suitably.
The manufacturing method of the said polyester polyol is not specifically limited, A well-known method is employable.

  As the aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, metaphthalic acid, naphthalenedicarboxylic acid and the like are preferably mentioned because a composition having excellent adhesion to polyimide can be obtained. These may be used alone or in combination of two or more. Among these, terephthalic acid is preferable because higher adhesiveness can be obtained.

In addition, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and long chain dicarboxylic acid may be used in combination with the aromatic dicarboxylic acid.
The long-chain dicarboxylic acid is a dicarboxylic acid having 20 or more carbon atoms, and examples thereof include eicosane diacid, docosane diacid, and dimer acid.

As the polyol compound used for the polyester polyol, known polyol compounds used for the production of polyester can be used without particular limitation, and examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, and long chain glycol. . These may be used alone or in combination of two or more.
The long chain glycol is a glycol having a weight average molecular weight of 400 to 6000, and examples thereof include polyethylene glycol, poly (1,3-propylene glycol), and polytetramethylene glycol.

  Examples of the polyisocyanate compound include TDI such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate; MDI such as diphenylmethane-4,4′-diisocyanate; tetramethylxylylene diisocyanate (TMXDI), trimethyl Hexamethylene diisocyanate (TMHMDI), 1,5-naphthalene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), triphenylmethane triisocyanate, Examples thereof include diisocyanate (NBDI) having a norbornane skeleton and modified products thereof. These may be used alone or in combination of two or more. Among these polyisocyanate compounds, HDI, XDI, and IPDI are preferable from the viewpoint of excellent heat resistance.

  The method for producing the polyester urethane is not particularly limited, and can be produced according to a known method using the polyester polyol and the polyisocyanate compound as raw materials. Preferably, the polyester polyol and the polyisocyanate compound are mixed and reacted so that the obtained polyester urethane has a carboxy group having an acid value of 5 KOH mg / g or less.

The polyester urethane has an acid value of 5 KOHmg / g or less. When the acid value exceeds 5 KOHmg / g, the storage stability and the adhesion to polyimide are poor. The reason is considered to be that when the carboxy group of the polyester urethane reacts with the epoxy resin (A) during storage, it cannot exhibit adhesiveness when bonded to the polyimide film.
The acid value of the polyester urethane is preferably 3 KOHmg / g or less, and more preferably 0 KOHmg / g (that is, having no carboxy group).

The weight average molecular weight of the polyester urethane is preferably more than 100,000 from the viewpoint of excellent bending resistance. The weight average molecular weight of the polyester urethane is more preferably more than 150,000 and even more preferably 200,000 or more from the viewpoint of making the coating more tough.
The weight average molecular weight of the polyester urethane is preferably 1,000,000 or less from the viewpoint that compatibility with other components is not impaired.

  The polyester urethane has a glass transition temperature (Tg) of preferably 0 ° C. or higher, more preferably 10 ° C. or higher, from the viewpoint of excellent heat resistance.

  Moreover, the said polyester urethane can also use a commercial item. For example, Byron UR1400 manufactured by Toyobo Co., Ltd. is preferable because it has excellent adhesion to polyimide.

  The content of the polyester urethane is preferably 1 to 65 parts by mass, more preferably 5 to 60 parts by mass, and 10 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin (A). Is more preferable. When the content of the polyester urethane is within this range, it can be cured at a low temperature and in a short time, and furthermore, it has excellent adhesion to polyimide and wet heat resistance.

  The polyether ester amide is a polymer having an amide bond, an ether bond and an ester bond in the main chain, and can be obtained by reacting a polyamide component and a polyether ester component. As polyether ester amide, what was described in Unexamined-Japanese-Patent No. 2003-206428 can be used conveniently, for example.

Examples of the polyamide component used for the production of the polyether ester amide include tetramethylene diamine, hexamethylene diamine, 2,2,4 or 2,4,4-trimethylhexamethylene diamine, and bis (4-aminocyclohexyl) methane. Aliphatic, alicyclic or aromatic diamines such as bis (4-amino-3-methylcyclohexyl) methane, phenylenediamine, and xylylenediamine, and adipic acid, azelaic acid, sebacic acid , Dodecanedioic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, a polyamide produced from an aliphatic, alicyclic or aromatic dicarboxylic acid having 6 or more carbon atoms such as polymerized fatty acid; ω-aminocaproic acid, ω -Aminoenanoic acid, ω-aminocaprylic acid, 11-aminounde A polyamide produced from an aminocarboxylic acid having 6 or more carbon atoms such as acid and 12-aminododecanoic acid; a polyamide produced from a lactam having 6 or more carbon atoms such as caprolactam, enantolactam, capryllactam, laurolactam; These copolyamides or mixed polyamides thereof can be mentioned.
Among these, polyamide produced from hexamethylenediamine and adipic acid, polyamide produced from hexamethylenediamine and polymerized fatty acid and azelaic acid or sebacic acid, polyamide produced from 12-aminododecanoic acid, produced from caprolactam Polyamides are preferred.

  As the polymerized fatty acid, an unsaturated fatty acid, for example, a polymerized fatty acid obtained by polymerizing a monobasic fatty acid having at least one double bond or triple bond having 10 to 24 carbon atoms is used. Specific examples include dimers such as oleic acid, linoleic acid, and erucic acid.

A commercially available polymerized fatty acid usually contains a dimerized fatty acid as a main component and also contains a raw material fatty acid and a trimerized fatty acid, but the dimerized fatty acid content is 70% by mass or more, preferably It is preferably 95% by mass or more, and further, hydrogenated to lower the degree of unsaturation.
Specifically, for example, a pre-pole 1009, a pre-pole 1004, a pre-pole 1010 (manufactured by Unikema) or an empole 1010 (manufactured by Henkel) are preferably exemplified.

  The weight average molecular weight of the polyamide described above is preferably 5,000 to 50,000, more preferably 5,000 to 30,000, from the viewpoint of increasing the cohesive force of the resin and increasing the adhesion. More preferably, it is 20,000-20,000.

  The polyether ester component used for the production of the polyether ester amide can be obtained by reacting a polyoxyalkylene glycol and a dicarboxylic acid.

Examples of the polyoxyalkylene glycol include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. Examples thereof include a polymer and a copolymer of a dihydric phenol compound and the above polyoxyalkylene glycol.
These polyoxyalkylene glycols preferably have a number average molecular weight of 200 to 3,000.

  The dicarboxylic acid is preferably a dicarboxylic acid having 6 to 20 carbon atoms, for example, an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid or dodecanedioic acid; an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid. Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; and the like. In particular, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, and isophthalic acid are preferable from the viewpoint of polymerizability and properties of polyetheresteramide.

  The mass ratio of the polyamide component and the polyether ester component used in the production of the polyether ester amide is preferably 95/5 to 20/80. Within this range, the impact resistance, mechanical strength and heat resistance are excellent.

  The weight average molecular weight of the polyether ester amide is preferably 5,000 to 50,000, more preferably 5,000 to 30,000 from the viewpoint that the cohesive strength of the resin is increased and the adhesion is improved. Preferably, it is 10,000 to 20,000.

  The method for producing the polyether ester amide is not particularly limited. For example, a method of synthesizing a polyamide oligomer first, adding a polyoxyalkylene glycol and a dicarboxylic acid thereto, and heating under reduced pressure to increase the degree of polymerization. Can be mentioned.

  The polyester amide is a polymer having an amide bond and an ester bond in the main chain other than the polyether ester amide described above, and can be obtained by reacting polyamide and polyester. As the polyester amide, for example, those described in JP-A No. 2002-3601 can be suitably used.

  As the polyesteramide, a copolyamide component (a) having a polyamide unit (a-1) represented by the following formula (1) and a polyamide unit (a-2) represented by the following formula (2); Preferable examples include polyester amides obtained by copolymerization with a polyester component (b) having a repeating unit represented by the following formula (3).

In the above formula, R ¹ and R ³ each independently represent a residue obtained by removing an amino group from an aliphatic diamine or alicyclic diamine having 6 to 44 carbon atoms.
R ² represents a residue obtained by removing a carboxy group from an aliphatic or aromatic dicarboxylic acid having 6 to 22 carbon atoms.
R ⁴ represents a residue obtained by removing a carboxy group from a polymerized fatty acid mainly composed of a dimer acid (dimerized fatty acid) having 20 to 48 carbon atoms.

R ⁵ represents a residue obtained by removing a hydroxy group from a substituted or unsubstituted aliphatic or alicyclic diol having 2 to 54 carbon atoms.
R ⁶ is a polymerized fatty acid mainly composed of a residue obtained by removing a carboxy group from an aliphatic or aromatic dicarboxylic acid having 6 to 22 carbon atoms, or a dimer acid (dimerized fatty acid) having 20 to 48 carbon atoms. Represents a residue obtained by removing a carboxy group from

  The above-mentioned polyesteramide is a polymerized fatty acid and / or a derivative thereof having at least 20 to 48 carbon dimer acid (dimerized fatty acid) derived from a natural fatty acid (including dimer diol and dimer diamine as derivatives). It is preferable that the residue derived from (included) is contained in the range of 10 to 90% by mass as the component amount.

Examples of the aliphatic diamine or alicyclic diamine having 6 to 44 carbon atoms used for producing the polyamide unit (a-1) include hexamethylene diamine, tetramethylene diamine, nonamethylene diamine, undecamethylene diamine, and dodeca. Aliphatic diamines such as methylenediamine, methylpentamethylenediamine, 2,2,4 (or 2,4,4) -trimethylhexamethylenediamine, dimerized amine derived from polymerized fatty acid having 20 to 48 carbon atoms; bis- ( 4,4'-aminocyclohexyl) methane, metaxylylenediamine, paraxylylenediamine, alicyclic diamines such as isophoronediamine and norbornanediamine; and the like, and one kind or a mixture of two or more kinds may be used. .
In particular, alicyclic diamines are preferable from the viewpoint of excellent solubility and mechanical properties of polyesteramide in a solvent.

Examples of the aliphatic or aromatic dicarboxylic acid having 6 to 22 carbon atoms and ester derivatives thereof used for the production of the polyamide unit (a-1) include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Dodecadioic acid, hexadecanedioic acid, eicosandioic acid, eicosadienedioic acid, diglycolic acid, 2,2,4-trimethyladipic acid, xylenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid And ester derivatives thereof and the like, and one or a mixture of two or more thereof may be used.
In particular, azelaic acid, sebacic acid, and dodecadioic acid are preferable from the viewpoint of excellent solubility and mechanical properties of polyesteramide in a solvent.

  As a C6-C44 aliphatic diamine or alicyclic diamine used for manufacture of a polyamide unit (a-2), 1 type or 2 types chosen from the diamine illustrated to the polyamide unit (a-1) The above mixture is preferably used.

  As the polymerized fatty acid and its derivative mainly composed of a dimer acid (dimerized fatty acid) having 20 to 48 carbon atoms used for the production of the polyamide unit (a-2), a double having 10 to 24 carbon atoms is mainly used. A polymerized fatty acid obtained by polymerizing a monobasic unsaturated fatty acid having at least one bond or triple bond is used. For example, natural animal vegetable oil fatty acids such as soybean oil fatty acid, tall oil fatty acid, rapeseed oil fatty acid, polymerized fatty acids polymerized from oleic acid, linoleic acid, erucic acid and the like obtained by purifying them, and ester derivatives thereof.

Commercially available polymerized fatty acids usually contain dimer acid (dimerized fatty acid) as the main component, but also contain fatty acids as raw materials and fatty acids higher than trimer, but dimer acid (dimerized fatty acid). It is desirable that the content is 70% by mass or more, preferably 95% by mass or more, and the degree of unsaturation is reduced by hydrogenation.
In particular, commercially available products such as Prepole 1004, 1009, Prepole 1010 (manufactured by Unikema) and Empor 1008 (manufactured by Cognis) are preferred. Mixtures and ester derivatives thereof are also preferred.

The copolyamide component (a) used in the present invention has a copolymerization ratio of the polyamide unit (a-1) and the polyamide unit (a-2) in the range of 95/5 to 40/60 by mass ratio. Preferably it is done. More preferably, the copolymerization ratio of polyamide unit (a-1) / polyamide unit (a-2) is in the range of 90/10 to 50/50 in terms of mass ratio.
Within this range, the compatibility between the copolyamide component (a) and the polyester component (b), the copolyamide component (a) cohesion (crystallinity), and the adhesion of the resulting composition to polyimide are excellent.

Examples of the substituted or unsubstituted aliphatic or alicyclic diol having 2 to 54 carbon atoms used for the polyester component (b) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3 -Pentanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl- Aliphatic polyhydric alcohols such as 1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol; cyclopentadiene-1,2-diol, cyclohexane- And alicyclic polyhydric alcohols such as 1,3-diol, cyclohexane-1,4-diol and cyclohexane-1,4-dimethanol; dimer diol obtained by reducing dimer acid (dimerized fatty acid); 1 type or a 2 or more types of mixture may be sufficient.
In particular, ethylene glycol, 1,4-butanediol, neopentyl glycol, and dimer diol are preferred from the viewpoint of excellent solubility and mechanical properties of polyesteramide in a solvent. Examples of the dimer diol that is a derivative of a polymerized fatty acid that is preferably used include commercially available products such as Vespol HP-1000 (manufactured by Toagosei Co., Ltd.), Pripol 2033 (manufactured by Unikema), and Speziol C36 / 2 (manufactured by Cognis).
In the present specification, the term “polymerized fatty acid derivative” may contain the dimer diol as described above.

  Polymerized fatty acid mainly composed of an aliphatic or aromatic dicarboxylic acid having 6 to 22 carbon atoms and an ester derivative thereof, or a dimer acid (dimerized fatty acid) having 20 to 48 carbon atoms used in the polyester component (b). And as this derivative, the 1 type, or 2 or more types of mixture chosen from the compound illustrated as a raw material of a polyamide unit (a-1) and a polyamide unit (a-2) is used suitably.

In the polyester component (b) of the present invention, a polymerized fatty acid mainly composed of dimer acid (dimerized fatty acid) or a derivative thereof (the derivative includes dimer diol and dimer diamine) is introduced into the component. It is not particularly limited as long as it is a system.
The polyester component (b) is mainly composed of a substituted or unsubstituted aliphatic diol and / or alicyclic diol having 2 to 6 carbon atoms and a dimer acid (dimerized fatty acid) having 20 to 48 carbon atoms. A polyester component obtained from a polymerized fatty acid and its ester derivative, an aliphatic dicarboxylic acid or aromatic dicarboxylic acid having 6 to 22 carbon atoms and an ester derivative thereof, and a dimer acid (dimerized fatty acid having 20 to 48 carbon atoms) A polyester component composed of a dimer diol derived from a polymerized fatty acid containing as a main component is preferably mentioned.

However, the constituent ratio of the polymerized fatty acid contained in the polyester component (b) or its derivative component (the derivative also includes dimer diol and dimer diamine) is the same as the constituent of the polymerized fatty acid used in the copolyamide component (a) or this derivative. It is preferable that it is 10-90 mass% in the polyesteramide copolymer obtained including a ratio. More preferably, the constituent ratio of the dimer acid (dimerized fatty acid) or the derivative component thereof is 20 to 80% by mass in the obtained polyesteramide.
Within this range, the solubility of polyesteramide in a solvent, water resistance, flexibility, adhesion to polyimide, etc. are excellent.

  The polyesteramide has a copolyamide component (a) / polyester component (b) copolymerization ratio of preferably 95/5 to 50/50, more preferably 90/10 to 60/40 in terms of mass ratio. A polymerized product is preferably used. Within this range, the adhesion to polyimide, heat and humidity resistance, bending resistance and pigment dispersibility are excellent.

  As the polyesteramide, the copolyamide component (a) and the polyester component (b) are linked by an ester bond or an amide bond, and at least one terminal group of the molecular chain formed continuously is a hydroxy group and / or a carboxy group. Those having a reaction terminated with a group, that is, those having a hydroxy group and / or a carboxy group at the terminal are preferred from the viewpoint of excellent adhesion to polyimide and resistance to moist heat.

  The weight average molecular weight of the polyester amide is preferably 5,000 to 50,000, more preferably 5,000 to 30,000 from the viewpoint of increasing the cohesive force of the resin and increasing the adhesiveness. More preferably, it is 10,000 to 20,000.

The polyester amide can be synthesized by a known method or the like.
For example, the copolyamide component can be advanced by a polycondensation reaction to synthesize a copolyamide having a functional group at the terminal and then polymerize the polyester component in the presence of the copolyamide. This polycondensation reaction is usually carried out by allowing the amidation reaction to proceed as the first stage and the esterification reaction to proceed to the second stage.

  In the amidation reaction, the components of the polyamide unit (a-1) and the polyamide unit (a-2) are blended so as to have a predetermined ratio, and then the temperature is raised and water generated by the polycondensation reaction is removed from the system. While removing, the polymerization proceeds in the reaction temperature range of 180 ° C. to 270 ° C. until the terminal functional group concentration reaches a predetermined concentration. The copolyamide obtained by the above reaction is preferably terminated at least at one terminal group with a carboxyl group or an amino group.

After the amidation reaction is completed, the esterification reaction is performed by a polycondensation reaction after blending the polyester component so that the ratio of the copolyamide having a functional group at the terminal to the polyester component becomes a predetermined ratio. Esterification is allowed to proceed in the reaction temperature range of 180 ° C. to 270 ° C. while removing the water to be removed from the system.
The reaction between the copolyamide component and the polyester component is preferably allowed to proceed in a transparent and homogeneous solution state. In a non-uniform and cloudy state, the reaction does not proceed efficiently.
Thus, in order to make a copolyamide component and a polyester component react efficiently, it is preferable to advance reaction under reduced pressure, Preferably it is 10 mmHg or less. When the reaction temperature is less than 180 ° C., the reaction rate is low and the polymerization viscosity of the system is high, so that an efficient polycondensation reaction becomes difficult. On the other hand, when the reaction temperature exceeds 270 ° C., decomposition and coloring reaction tend to occur, which is not preferable.

In the esterification reaction, an esterification catalyst can be used to efficiently advance the reaction.
The catalyst is not particularly limited, for example, lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tungsten, tin, antimony, cerium, boron, Metals such as manganese and zirconium; organometallic compounds; organic acid salts; metal alkoxides; metal oxides; More preferred are tetrabutoxy titanium, calcium acetate, zirconium carbonate, zirconium acetate, zirconyl stearate, diacyl stannous, tetraacyl stannic, dibutyl tin oxide, dibutyl tin dilaurate, dibutyl tin malate, tin dioctanoate, tin. Examples include tetraacetate, triisobutylaluminum, tetrabutyltitanate, tetrapropoxytitanate, titanium (oxy) acetylacetonate, germanium dioxide, tungstic acid, and antimony oxide. These may be used alone or in combination of two or more.

In the polymerization reaction of the polyesteramide, a stabilizer can be used in combination for the purpose of preventing oxidative decomposition, thermal decomposition and colorability from any stage.
Such a stabilizer is not particularly limited, and examples thereof include N, N′-hexamethylenebis (3,3-di-t-butyl-4-hydroxy-hydrocinnamide), triethylene glycol. -Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 -Hydroxybenzyl) benzene, 3,9-bis {2- [3- (3-t-butyl-4hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl} -2,4 Hindered phenolic antioxidants such as 8,10-tetraoxaspiro [5,5] undecane; tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, 2-t-butyl Ru-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, dimyristyl-3,3′-thiodipropionate, pentaerythrityltetrakis (3-laurylthio) Heat stabilizers such as propionate) and ditridecyl-3,3'-thiodipropionate. These may be used alone or in combination of two or more.

  The content of the polyether ester amide and / or the polyester amide (the amount when only one of the polyether ester amide and the polyester amide is contained, the total amount when both are contained) is the epoxy resin (A ) It is preferably 1 to 65 parts by mass, more preferably 5 to 60 parts by mass, and still more preferably 10 to 50 parts by mass with respect to 100 parts by mass. When the content of the polyether ester amide and / or the polyester amide is within this range, the composition can be cured at a low temperature and in a short time, and further, it has excellent adhesion to polyimide and heat and moisture resistance.

It is preferable that the composition of this invention contains a hardening | curing agent other than each component mentioned above.
Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, thiol compounds, imidazoles, boron trifluoride-amine complexes, guanidine derivatives, and the like. Amine compounds, acid anhydride compounds, thiol compounds, and the like are preferable.

  Specific examples of amine compounds include metaxylylenediamine (MXDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), norbornanediamine (NBDA), diaminodiphenylmethane, diethylenetriamine, and triethylene. Examples include amine compounds such as tetramine, tetraethylenepentamine, diaminodiphenylsulfone, isophoronediamine (IPDA), dicyandiamide, dimethylbenzylamine, ketimine compounds, and polyamines of polyamide skeleton synthesized from dimer of linolenic acid and ethylenediamine. It is done. Among them, metaxylylenediamine (MXDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), norbornanediamine (NBDA), triethylenetetramine, etc. are liquid at room temperature, have good workability, and are curable. Is preferable from the viewpoint of high.

  Examples of the acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl And hexahydrophthalic anhydride. Among these, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like are preferable because they are liquid at room temperature, have good workability, and have high curability.

  Specific examples of phenolic compounds include polycondensates of bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes, phenols, and the like. Examples thereof include polymers with various diene compounds, polycondensates of phenols and aromatic dimethylol, or condensates of bismethoxymethylbiphenyl with naphthols or phenols, biphenols and modified products thereof.

Specific examples of the thiol-based curing agent include 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1 , 4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, 1,9-nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol, 1, 2-propanedithiol, 1,3-propadithiol, toluene-3,4-dithiol, 3,6-dichloro-1,2-benzenedithiol, 1,3,5-triazine-2,4,6-trithiol (tri Mercapto-triazine), 1,5-naphthalenedithiol, 1,2-benzenedimethanethiol, 1,3-benzenedimethyl Thiol, 1,4-benzenedimethanethiol, 4,4′-thiobisbenzenethiol, 2-di-n-butylamino-4,6-dimercapto-s-triazine, trimethylolpropane tris (β-thiopropio Nate), 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6-dioxaoctane, 1,5-dimercapto-3-thiapentane, Epomate QX10 (manufactured by Japan Epoxy Resin Co., Ltd.) Dithiols such as Epomate QX11 (manufactured by Japan Epoxy Resin Co., Ltd.);
Examples include thiol compounds such as polythiol such as Thiocol (manufactured by Toray Fine Chemical Co., Ltd.), Cup Cure 3-800 (manufactured by Japan Epoxy Resin Co., Ltd.), and EpiCure QX40 (manufactured by Japan Epoxy Resin Co., Ltd.). Among these, epoxide QX10, epoxide QX11, cup cure 3-800, epicure QX40 and the like are suitably used as commercially available fast-curing polythiols.

As said hardening | curing agent, it can be set as 1 liquid type curable resin composition, and a latent hardening | curing agent is used suitably from the point which is excellent in workability | operativity. Examples of the latent curing agent include a moisture latent curing agent that allows the resin to be cured by contact with moisture, and a thermal latent curing agent that allows the resin to be cured by heating.
Examples of moisture latent curing agents include ketimine compounds and oxazolidine compounds.
Examples of the thermal latent curing agent include those obtained by coating a curing agent such as amine with a resin such as an epoxy resin (for example, NOVACURE manufactured by Asahi Kasei Corporation).

  0.8-1.1 equivalent is preferable with respect to 1 equivalent of epoxy groups in a composition, and, as for the usage-amount of a hardening | curing agent, 0.95-1.05 equivalent is more preferable.

Moreover, the composition of this invention may contain a curing catalyst as needed.
Specific examples of the curing catalyst include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 2,4,6- Tertiary amines such as tris (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, metal compounds such as tin octylate, And quaternary phosphonium salts.

  0.5-10 mass parts is preferable with respect to 100 mass parts of epoxy resins (A), and, as for content of a curing catalyst, 1-5 mass parts is more preferable.

  Moreover, it is one of the preferable aspects that the composition of this invention contains a phenoxy resin further. In the case of containing a phenoxy resin, the film forming property is improved, and adhesion can be performed in a shorter time.

  The weight average molecular weight of the phenoxy resin is preferably 1,000 to 10,000, and more preferably 2,000 to 6,000, from the viewpoint of excellent film forming properties.

  The content of the phenoxy resin is preferably 1 to 80 parts by mass and more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the epoxy resin (A).

  The composition of the present invention is provided with a filler, a solvent, a reaction retarding agent, an anti-aging agent, an antioxidant, a pigment (dye), a plasticizer, and a thixotropic agent, as long as the effects of the present invention are not impaired. Various additives such as an agent, an ultraviolet absorber, a flame retardant, a surfactant (including a leveling agent), a dispersant, a dehydrating agent, an adhesion-imparting agent, and an antistatic agent can be contained.

  Examples of the filler include organic or inorganic fillers having various shapes. Specifically, for example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; Waxite clay, kaolin clay, calcined clay; carbon black; these fatty acid treated products, resin acid treated products, urethane compound treated products, and fatty acid ester treated products.

  Examples of the solvent include, but are not limited to, aromatic hydrocarbons such as benzene, xylene, and toluene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and butyl acetate; diethyl ether , Ethers such as tetrahydrofuran and dioxane, and the like. These may be used alone or in combination of two or more.

  The production method of the composition of the present invention is not particularly limited. For example, a method in which each of the above essential components and optional components is placed in a reaction vessel and sufficiently kneaded using a stirrer such as a mixing mixer under reduced pressure. Can be used.

The composition of the present invention described above can be cured at a low temperature for a short time (for example, at 160 ° C. for 20 seconds), and is excellent in adhesion to polyimide and heat and moisture resistance.
The reason why it can be cured at a low temperature for a short time is considered to be because it contains a terpolymer (B) or a polymer (C) having a high film-forming property.
The reason for excellent adhesion to polyimide and wet heat resistance is that the epoxy resin (A), ternary copolymer (B) and polymer (C) have excellent compatibility and can be uniformly dispersed, so the state of the adhesive interface is good. This is considered to be because of the interaction between the amide bond and the like contained in the resin component and the polyimide film.
Therefore, the composition of the present invention is suitably used as an adhesive for bonding polyimide materials together or a polyimide material and another material.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
(Examples 1 to 6, Reference Example 7, Examples 8 to 11 and Comparative Examples 1 to 6)
The components shown in Table 1 below were mixed using a stirrer in the proportions (parts by mass) shown in Table 1 to obtain the compositions shown in Table 1.
About each obtained composition, the adhesiveness (initial stage) with respect to a polyimide and heat-and-moisture resistance were evaluated by the method shown below.
The results are shown in Table 1. In addition, although the polyesterurethane (C1) and the polyesterurethane 1 in Table 1 are solvent mixture products, these compounding quantities are shown by the amount of solid content.

<Adhesiveness to polyimide (initial)>
Prepare two polyimide films (Kapton (registered trademark), manufactured by Toray DuPont, 25 μm thick), apply each composition to one polyimide film, and dry it in an oven at 80 ° C. for 5 minutes to remove the solvent. Removed. Next, after bonding the other polyimide film to the composition application surface of this film and bonding it by hot pressing for 20 seconds under the conditions of 3 MPa and 160 ° C., the sample was cut into a 1 cm width to prepare a test piece. .
The obtained test piece was subjected to a 180 ° peel test at a test temperature of 23 ° C. and a tensile speed of 50 mm / min using a peel tester (manufactured by Imada Co., Ltd.), and the peel strength was measured. This value was defined as the peel strength (initial).

<Heat and heat resistance>
After leaving the test piece produced in the same manner as the above <adhesiveness to polyimide (initial)> for 500 hours under the conditions of 85 ° C. and 85% RH, the peel strength was measured by the same measuring method as described above.

The compounding amounts in Table 1 are all solid contents.
Each component in Table 1 is as follows.
-Epoxy resin (A): Epicron HP4032D, manufactured by Dainippon Ink & Chemicals, Inc.-Terpolymer (B1): E40, manufactured by Arkema,-(S) _n- (B) _m- (M) _l- A mixture of a block copolymer having an SBM structure represented by the block copolymer having an MBS structure represented _by- (M) _o- (B) _p- (S) _q- , S: B: M = (n + q ): (M + p): (l + o) = 0.47: 0.26: 0.27, weight average molecular weight 5000 to 50000
-Ternary copolymer (B2): A-012, manufactured by Arkema,-(S) _n- (B) _m- (M) _l -and a block copolymer having an SBM structure represented by-(M) _o- (B) _p- (S) _q- with a block copolymer having an MBS structure represented by S-B: M = (n + q) :( m + p) :( l + o) = 0.16: 0 .41: 0.43, weight average molecular weight 5000 to 50000

Core-shell type rubber particles 1: BTA751, Rohm & Haas, a core-shell type comprising a core composed of a styrene-butadiene copolymer and a shell composed of polymethyl methacrylate covering the core. Rubber particles Polyester urethane (C1): Polyester urethane containing a structure derived from terephthalic acid, Byron UR1400, manufactured by Toyobo Co., Ltd., acid value of less than 1 KOHmg / g, weight average molecular weight 110,000, glass transition temperature 83 ° C., resin solid Concentration 30% by mass (solvent methyl ethyl ketone / toluene = 50/50)
Polyester urethane 1: Polyester urethane containing a structure derived from terephthalic acid, Byron UR3500, manufactured by Toyobo Co., Ltd., acid value 35 KOH mg / g, weight average molecular weight 110,000, glass transition temperature 10 ° C., resin solid content concentration 40% by mass (Solvent Toluene)
Polyether ester amide block copolymer (C2): TPAE-32, manufactured by Fuji Kasei Kogyo Co., Ltd. Polyester amide block copolymer (C3): TPAE-617, manufactured by Fuji Kasei Kogyo Co., Ltd. Phenoxy resin: phenototo YP- 50, manufactured by Toto Kasei Co., Ltd. Latent curing agent: NovaCure 3941, Asahi Kasei Co., Ltd., containing 70% by mass of epoxy resin Silica: Excelica UF-103, manufactured by Tokuyama Co., Ltd.

As is apparent from the results shown in Table 1, Comparative Example 3, which does not contain a styrene-butadiene-methyl methacrylate terpolymer, has low adhesion to polyimide and heat and moisture resistance. In Comparative Examples 1 and 4 to 6 containing core-shell type rubber particles instead of the styrene-butadiene-methyl methacrylate terpolymer, the adhesion to polyimide and the heat-and-moisture resistance were somewhat improved, but this was not sufficient. Moreover, the comparative example 2 containing polyester urethane with a high acid value had low adhesiveness with respect to a polyimide, and heat-and-moisture resistance.
Examples 1 to 6 and 8 to 11 showed high adhesion to polyimide under curing conditions of 160 ° C. and 20 seconds, and were excellent in heat and moisture resistance.

Claims (1)

At least selected from the group consisting of epoxy resin (A), styrene-butadiene-methyl methacrylate terpolymer (B), polyester urethane having an acid value of 5 KOHmg / g or less, polyether ester amide, and polyester amide 1 type of polymer (C),
The content of the styrene-butadiene-methyl methacrylate terpolymer (B) is 1 to 65 parts by mass with respect to 100 parts by mass of the epoxy resin (A),
Content of the said polyester urethane is 1-65 mass parts with respect to 100 mass parts of said epoxy resins (A),
Content of the said polyetheresteramide and / or polyesteramide is 1-65 mass parts with respect to 100 mass parts of said epoxy resins (A),
Does not contain polyester urethane with an acid value of more than 5 KOHmg / g ,
In addition, it contains a curing agent,
A curable resin composition , wherein the curing agent is a latent curing agent .