JPWO2008143128A1 - Resin composition and film-forming material containing the same - Google Patents

Abstract

The resin composition of the present invention comprises (A) component: a resin having an acid anhydride group and / or carboxyl group, (B) component: an epoxy resin, and (C) component: a filler containing hydrotalcite. It is characterized by containing. The component (A) preferably has a polycarbonate skeleton. Furthermore, the following general formula (1): (In the formula (1), a plurality of R's each independently has 1 to 18 carbon atoms. A plurality of X's each independently represents an alkylene group having 1 to 18 carbon atoms or an arylene group, and m and n each independently represents an integer of 1 to 20). It is preferable to contain. ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can be used conveniently for screen printing, can reduce the sticking property to the polyimide film of a hardened film, and can reduce the black swelling of the electrode by electricity supply under high temperature and high humidity, and a film containing the same Forming materials can be provided.

Description

  The present invention relates to a resin composition and a film-forming material containing the same, and more particularly to a resin composition having thixotropy suitable for a coating method such as a screen printer, a dispenser, a spin coater, and a film-forming material containing the same.

  In recent years, in the field of electronic components, in response to miniaturization, thinning, and high speed, as a resin for film forming materials having excellent heat resistance, electrical characteristics, and moisture resistance, polyimide resin, polyamide instead of epoxy resin Imide resin and polyamide resin are used. However, these resins have a rigid resin structure, and when used as a thin film substrate, the cured substrate is greatly warped, and the cured film lacks flexibility and has poor flexibility.

  Therefore, in order to improve the above-described warpage and flexibility, a polyamide-imide resin that has been modified to have a flexible and low elastic modulus by modifying the resin (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3) is proposed. Has been. In these resins, in order to improve printability and workability, inorganic fillers, organic fillers, and the like are dispersed in the resin solution. In addition, additives such as various coupling agents and surface treatment agents are used to improve the adhesion between the substrate and the resin or between the filler and the resin.

JP 62-106960 A Japanese Patent Laid-Open No. 8-12763 JP-A-7-196798

  However, when winding the above film-forming material on the surface of the copper wiring side of the flexible wiring board in which the copper wiring is applied on one side of the polyimide film and then winding the cured film, the copper wiring of the flexible wiring board There is a problem that a cured film made of a film-forming material adheres to the surface on which the film is not applied. Conventionally, a spacer is provided between the polyimide film and the cured film.

  In addition, when a circuit board having a cured film formed using the film-forming material disclosed in Patent Documents 1 to 3 is energized under high temperature and high humidity, black swelling of the electrode occurs, which is a cause of lowering electrical characteristics. There is concern about it.

  The present invention has been made in view of the above-described conventional circumstances, and the problem is that the adhesion between the cured film and the polyimide film can be reduced, and the black swelling of the electrode can be reduced in energization under high temperature and high humidity. An object of the present invention is to provide a resin composition that can be formed and a film-forming material containing the resin composition.

  In order to solve the above-mentioned problems, the resin composition according to the present invention comprises (A) component: a resin having an acid anhydride group and / or carboxyl group, (B) component: epoxy resin, and (C) component: And a filler containing hydrotalcite.

In the resin composition having the above configuration, the component (A) preferably has a polycarbonate skeleton.
Furthermore, the component (A) is represented by the following general formula (1)

（式（１）中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基を示し、複数個のＸは、それぞれ独立に炭素数１〜１８のアルキレン基又はアリーレン基を示し、ｍ及びｎは、それぞれ独立に１〜２０の整数を示す）で表される構成単位を含むことが好ましい。

(In the formula (1), a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, and a plurality of X's each independently represents an alkylene group or arylene group having 1 to 18 carbon atoms, It is preferable that m and n contain the structural unit represented by the integer of 1-20 each independently.

  Further, the component (A) is a trivalent or higher polycarboxylic acid having an isocyanate residue and an acid anhydride group of at least one resin selected from a polyimide resin having a polycarbonate skeleton, a polyamideimide resin, and a polyamide resin. A resin obtained by reacting the derivative is preferable.

  Moreover, in the resin composition of the said structure, content of (C) component is 10-50 mass% with respect to 100 weight part of (A) component, and the hydrotalcite which occupies in said (C) component The content is preferably 10 to 50% by mass.

  Moreover, the resin composition of this invention is used suitably for the protective film use of the flexible printed circuit board which laminated | stacked copper foil on the polyimide base material.

  The film forming material of the present invention includes the resin composition of the present invention.

  The resin composition of the present invention is suitable for electronic components such as flexible wiring boards because it can reduce the adhesion between the cured film and the polyimide film, and can reduce the black swelling of the electrode when energized under high temperature and high humidity. The electronic component can be used in a highly reliable electronic component.

  As described above, the resin composition of the present invention comprises (A) component: resin having an acid anhydride group and / or carboxyl group, (B) component: epoxy resin, and (C) component: hydrotalcite. And a filler containing the above as an essential component. Hereinafter, each essential component will be described in detail.

[(A) component: resin having acid anhydride group and / or carboxyl group]
As the “resin having an acid anhydride group and / or carboxyl group” as the component (A), an epoxy resin having a butadiene structure or a silicone structure, a phenol resin, an acrylic resin, a polyurethane, a polybutadiene, a water-added polybutadiene, a polyester, or a polycarbonate , Polyether, polysulfone, polytetrafluororesin, polysilicone, melamine resin, polyamide, polyamideimide, polyimide and other resins having an acid anhydride group and / or carboxyl group introduced into the main chain and / or side chain. It is done. These can be used alone or in combination of two or more. Further, a resin having an acid anhydride group and / or a carboxyl group and a resin having no acid anhydride group and / or a carboxyl group can be used in combination.

  Examples of the method for introducing the carboxyl group include epoxy resins having a butadiene structure or a silicone structure, phenol resins, acrylic resins, polyurethane, polybutadiene, water-added polybutadiene, polyester, polycarbonate, polyether, polysulfone, polytetrafluororesin, and polysilicone. In the synthesis process of melamine resin, polyamide, polyamideimide, polyimide resin, etc., it can be obtained by using a compound having a carboxyl group capable of radical polymerization, condensation polymerization or ion polymerization.

In addition, the acid anhydride group can be introduced by using an epoxy resin having a butadiene structure or a silicone structure, a phenol resin, an acrylic resin, a polyurethane, a polybutadiene, a water-added polybutadiene, a polyester, a polycarbonate, a polyether, a polysulfone, or a polytetrafluoro. Epoxy residues, isocyanate residues, hydroxyl groups and carboxyl groups derived from resins, polysilicones, melamine resins, polyamides, polyamideimides, polyimide resins, etc. and the following general formula (2) and / or general formula (3)
It can obtain by making it react with the compound represented by these.

（式（２）中、Ｚ^１は有機基を表し、Ｗは、水酸基、イソシネート基、カルボキシル基、エポキシ基、グリシジル基を表す。）

(In formula (2), Z ¹ represents an organic group, and W represents a hydroxyl group, an isocyanate group, a carboxyl group, an epoxy group, or a glycidyl group.)

（式（３）中、Ｚ^２は有機基を表し、Ｗは、水酸基、イソシネート基、カルボキシル基、エポキシ基、グリシジル基を表す。）

(In formula (3), Z ² represents an organic group, and W represents a hydroxyl group, an isocyanate group, a carboxyl group, an epoxy group, or a glycidyl group.)

  By introducing an acid anhydride group and / or carboxyl group into the terminal and / or side chain of the resin, the reactivity with the epoxy resin, which is the component (B) described later, is increased, so that the sticking property between the spacer and the solder resist is increased. Can be improved.

  In addition, the resin of the component (A) of the present invention is preferably flexible and has a low elastic modulus so as to mainly correspond to a flexible substrate. In order to make the resin of component (A) flexible and have a low elastic modulus, introduction of a component capable of improving flexibility into the main chain of the resin can be mentioned, and as such a component, for example, polybutadiene A skeleton, a silicone resin skeleton, and / or a polycarbonate skeleton are preferable.

  In order to improve the heat resistance, electrical properties, moisture resistance, solvent resistance and chemical resistance of the cured coating, it is possible to introduce a component capable of improving heat resistance into the main chain of the resin. As such a component, for example, polyimide, polyamideimide or polyamide or a skeleton thereof is preferable. Among these, a polycarbonate skeleton and an imide skeleton are preferable from the viewpoint of flexibility, low elastic modulus, and high heat resistance.

  In the present invention, the “resin having an acid anhydride group and / or carboxyl group” that can be used as the component (A) is usually 1,6-hexanediol-based polycarbonate diol and the like, a compound having a carboxyl group, It can be obtained by reacting a compound having an acid anhydride and / or a compound having an isocyanate group.

  In the present invention, “resin having an acid anhydride group and / or carboxyl group” that can be used as the component (A) is, for example, (a) component: trivalent polycarboxylic acid having an acid anhydride group. It can be obtained by reacting one or more compounds selected from acids and derivatives thereof and tetravalent polycarboxylic acids having an acid anhydride group and component (b): an isocyanate compound or an amine compound.

  Although the “trivalent polycarboxylic acid having an acid anhydride group and its derivative” as the component (a) is not particularly limited, for example, the following formulas (4) and (5):

（式（４）及び（５）中、Ｒ’は、水素、炭素数１〜１０のアルキル基又はフェニル基を示し、Ｙ¹は、−ＣＨ₂−、−ＣＯ−、−ＳＯ₂−、又は−Ｏ−である）で示される化合物を使用することができる。

(In the formulas (4) and (5), R ′ represents hydrogen, an alkyl group having 1 to 10 carbon atoms or a phenyl group, and Y ¹ represents —CH ₂ —, —CO—, —SO ₂ —, or -O-) can be used.

  As the “trivalent polycarboxylic acid having an acid anhydride group” as the component (a), trimellitic acid anhydride is particularly preferable from the viewpoint of heat resistance, cost, and the like.

  The other “tetravalent polycarboxylic acid having an acid anhydride group” is not particularly limited. For example, the following formula (6):

（式中、Ｙ²は、下記式（７）：

(In the formula, Y ² represents the following formula (7):

で示される複数の基から選ばれる基である）で示されるテトラカルボン酸二無水物を使用することができる。これらは、単独で又は２種類以上を組み合わせて使用することができる。

And a tetracarboxylic dianhydride represented by a plurality of groups represented by the formula (1) can be used. These can be used alone or in combination of two or more.

  In addition to these, as necessary, an aliphatic dicarboxylic acid (succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decanedioic acid, dodecanedioic acid, dimer acid, etc.) Aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, etc.) can be used in combination. In this case, an amide bond is also formed in the molecular chain.

  The isocyanate compound used as the component (b) is, for example, the following formula (8):

（式（８）中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基であり、Ｘは二価の有機基であり、ｍ及びｎは、それぞれ独立に１〜２０の整数である）で示されるジイソシアネート類を用いることができる（以下、化合物（ｂ−１）と記す場合もある）。

(In Formula (8), a plurality of R's are each independently an alkylene group having 1 to 18 carbon atoms, X is a divalent organic group, and m and n are each independently an integer of 1 to 20) Can be used (hereinafter sometimes referred to as compound (b-1)).

  The compound (b-1) represented by the above formula (8) is represented by the following formula (9):

（式（９）中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基であり、ｍは１〜２０の整数である）で示されるカーボネートジオール類と、下記式（１０）：
ＯＣＮ−Ｘ−ＮＣＯ （１０）
（式中、Ｘは、二価の有機基である）で示されるジイソシアネート類とを反応させることにより得られる。

(In the formula (9), a plurality of R's are each independently an alkylene group having 1 to 18 carbon atoms, and m is an integer of 1 to 20), and the following formula (10) :
OCN-X-NCO (10)
It is obtained by reacting with a diisocyanate represented by the formula (wherein X is a divalent organic group).

  Examples of the divalent organic group represented by X in the formula (10) include, for example, an alkylene group having 1 to 20 carbon atoms, or an unsubstituted or substituted lower alkyl group having 1 to 5 carbon atoms such as a methyl group. And an arylene group such as a phenylene group. The number of carbon atoms of the alkylene group is more preferably 1-18. Groups having two aromatic rings such as diphenylmethane-4,4'-diyl group and diphenylsulfone-4,4'-diyl group are also preferred.

  Examples of the carbonate diols represented by the above formula (9) include α, ω-poly (hexamethylene carbonate) diol, α, ω-poly (3-methyl-pentamethylene carbonate) diol, and the like. Examples of such products include trade names “PLACCEL CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL” manufactured by Daicel Chemical Industries, Ltd. These can be used alone or in combination of two or more.

  Examples of the diisocyanates represented by the above formula (10) include diphenylmethane-2,4′-diisocyanate; 3,2′-, 3,3′-, 4,2′-, 4,3′-, 5,2'-, 5,3'-, 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate; 3,2'-, 3,3'-, 4,2'- 4,3'-, 5,2'-, 5,3'-, 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate; 3,2'-, 3,3 ' -, 4,2'-, 4,3'-, 5,2'-, 5,3'-, 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate; diphenylmethane-4 , 4'-diisocyanate; diphenylmethane-3,3'-diisocyanate; diphenyl Diphenyl ether-4,4'-diisocyanate; benzophenone-4,4'-diisocyanate; diphenylsulfone-4,4'-diisocyanate; tolylene-2,4-diisocyanate; tolylene-2,6 -Diisocyanate; m-xylylene diisocyanate; p-xylylene diisocyanate; naphthalene-2,6-diisocyanate; 4,4 '-[2,2bis (4-phenoxyphenyl) propane] diisocyanate. In these diisocyanates, it is preferable to use an aromatic polyisocyanate in which X in the formula (8) has an aromatic ring. These can be used alone or in combination of two or more.

  Further, as the diisocyanates represented by the formula (10), within the scope of the object of the present invention, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, Aliphatic or alicyclic isocyanates such as transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, and lysine diisocyanate, or trifunctional or higher polyisocyanates can be used.

  Diisocyanates represented by the above formula (10) may be those stabilized with a blocking agent necessary to avoid changes over time. Examples of the blocking agent include alcohol, phenol and oxime, but there is no particular limitation.

  The mixing ratio of the carbonate diols represented by the above formula (9) and the diisocyanates represented by the above formula (10) is such that the ratio of the number of hydroxyl groups to the number of isocyanate groups is isocyanate group / hydroxyl group = 1.01 or more. It is preferable to do.

  The reaction of the carbonate diols represented by the above formula (9) and the diisocyanates represented by the above formula (10) can be carried out without solvent or in the presence of an organic solvent. The reaction temperature is preferably 60 to 200 ° C, more preferably 80 to 180 ° C. The reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and the like. For example, it can be 2 to 5 hours on a flask scale of 1 to 5 L (liter).

  The number average molecular weight of the compound (b-1) (isocyanate compound) thus obtained is preferably 500 to 10,000, more preferably 1,000 to 9,500, and 1,500. It is especially preferable that it is-9,000. When the number average molecular weight is less than 500, the warping property tends to be deteriorated. When the number average molecular weight exceeds 10,000, the reactivity of the isocyanate compound is lowered, and it tends to be difficult to obtain a polyimide resin.

In the present specification, the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. Moreover, the number average molecular weight and dispersion degree of this invention are defined as follows.
a) Number average molecular weight (M _n )
M _n = Σ (N _i M _i ) / N _i = ΣX _i M _i
(X _i = Mole fraction of molecules with molecular weight M _i = N _i / ΣN _i )
b) Weight average molecular weight M _w = Σ (N _i M _i ² ) / ΣN _i M _i = ΣW _i M _i
(W _i = weight fraction of molecules of molecular weight M _i = N _i M _i / ΣN _i M _i )
c) Molecular weight distribution (dispersity)
Dispersity = M _w / M _n

  As the isocyanate compound of the component (b), a compound other than the compound (b-1) (hereinafter referred to as compound (b-2)) can also be used. The compound (b-2) is not particularly limited as long as it is an isocyanate compound other than the compound (b-1), and examples thereof include diisocyanates represented by the above formula (9), trivalent or higher polyisocyanates, and the like. Can be mentioned. These can be used alone or in combination of two or more. The preferred range of the number average molecular weight of the isocyanate compound of the compound (b-2) is the same as that of the compound (b-1).

  In particular, from the viewpoint of heat resistance, it is preferable to use the compound (b-1) and the compound (b-2) in combination. In addition, when using a compound (b-1) and a compound (b-2) each independently, it is a compound (b-1) from points, such as a softness | flexibility as a protective film for flexible wiring boards, and a curvature improvement. Is preferably used.

  As compound (b-2), 50 to 100% by weight of the total amount is preferably aromatic polyisocyanate, and considering the balance of heat resistance, solubility, mechanical properties, cost, etc., 4, 4 '-Diphenylmethane diisocyanate is particularly preferred.

  When the compound (b-1) and the compound (b-2) are used in combination, the equivalent ratio of compound (b-1) / compound (b-2) is 0.1 / 0.9 to 0.9 / 0.1. Is preferable, 0.2 / 0.8 to 0.8 / 0.2 is more preferable, and 0.3 / 0.7 to 0.7 / 0.3 is particularly preferable. When the equivalence ratio is within this range, film properties such as good low warpage, adhesion and good heat resistance can be obtained.

  Among the components (b), examples of the amine compound include compounds obtained by converting the isocyanate group in the isocyanate compound of the component (b) to an amino group. Conversion of the isocyanato group to an amino group can be performed by a known method. The preferred range of the number average molecular weight of the amine compound is the same as that of the compound (b-1).

  In addition, the blending ratio of (a) component “trivalent polycarboxylic acid having acid anhydride group or derivative thereof and / or tetravalent polycarboxylic acid having acid anhydride group” is The ratio of the total number of carboxyl groups and acid anhydride groups in component (a) to the total number of isocyanate groups is preferably 0.6 to 1.4, and is preferably 0.7 to 1.3. More preferably, it is particularly preferably 0.8 to 1.2. When this ratio is less than 0.6 or exceeds 1.4, it tends to be difficult to increase the molecular weight of the resin containing polyimide bonds.

  When the compound represented by the formula (2) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (11):

（式（１１）中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基であり、Ｘは二価の有機基であり、ｍ及びｎは、それぞれ独立に１〜２０の整数である。）で示される繰り返し単位を有するポリアミドイミド樹脂を得ることができる。

(In Formula (11), a plurality of R's are each independently an alkylene group having 1 to 18 carbon atoms, X is a divalent organic group, and m and n are each independently an integer of 1 to 20) A polyamideimide resin having a repeating unit represented by the following formula can be obtained.

  When the compound represented by the formula (5) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (12):

（式（１２）中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基であり、Ｘは二価の有機基であり、ｍ及びｎは、それぞれ独立に１〜２０の整数であり、Ｙ¹は、−ＣＨ₂−、−ＣＯ−、−ＳＯ₂−、又は−Ｏ−である）で示される繰り返し単位を有するポリアミドイミド樹脂を得ることができる。

(In Formula (12), a plurality of R's are each independently an alkylene group having 1 to 18 carbon atoms, X is a divalent organic group, and m and n are each independently an integer of 1 to 20) And Y ¹ is —CH ₂ —, —CO—, —SO ₂ —, or —O—).

  When the compound represented by the above formula (6) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (13):

（式（１３）中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基であり、Ｘは二価の有機基であり、ｍ及びｎは、それぞれ独立に１〜２０の整数であり、Ｙ²は、前記式（７）で示される複数の基から選ばれる基である）で示される繰り返し単位を有するポリイミド樹脂を得ることができる。

(In Formula (13), a plurality of R are each independently an alkylene group having 1 to 18 carbon atoms, X is a divalent organic group, and m and n are each independently an integer of 1 to 20) Y ² is a group selected from a plurality of groups represented by the above formula (7)), and a polyimide resin having a repeating unit represented by the formula (7) can be obtained.

  In the present invention, component (a) in the process for producing “resin having an acid anhydride group and / or carboxyl group” used as component (A): a trivalent polycarboxylic acid having an acid anhydride group and derivatives thereof , And one or more compounds selected from tetravalent polycarboxylic acids having an acid anhydride group and the component (b): an isocyanate compound or an amine compound is an organic solvent, preferably a non-nitrogen-containing polar solvent In the presence of, it can be carried out by heating and condensing while removing carbon dioxide gas generated free from the reaction system.

  Examples of the non-nitrogen-containing polar solvent include ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, and sulfolane; Examples include ester solvents such as γ-butyrolactone and cellosolve acetate; ketone solvents such as cyclohexanone and methyl ethyl ketone; aromatic hydrocarbon solvents such as toluene and xylene, and the like. These may be used alone or in combination of two or more. be able to.

  It is preferable to select and use a solvent that dissolves the resin produced from the above solvents. After the synthesis, it is preferable to use a suitable paste solvent as it is. Γ-Butyrolactone is the most preferable because it is highly volatile, can impart low-temperature curability, and reacts efficiently in a homogeneous system.

  Moreover, it is preferable that the usage-amount of a solvent shall be 0.8-5.0 times (weight ratio) of resin containing the imide bond to produce | generate. If it is less than 0.8 times, the viscosity at the time of synthesis is too high, and the synthesis tends to be difficult due to the inability to stir. If it exceeds 5.0 times, the reaction rate tends to decrease.

  The reaction temperature is preferably 80 to 210 ° C, more preferably 100 to 190 ° C, and particularly preferably 120 to 180 ° C. If it is less than 80 ° C., the reaction time becomes too long, and if it exceeds 210 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed.

  If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.

  The polyamide resin, polyamideimide resin and polyimide resin obtained as described above have an isocyanate residue, and the isocyanate residue is reacted with the compound of the general formula (2) and / or the general formula (3). By making it, the resin which has an acid anhydride group can be obtained, the reactivity with the epoxy resin which is the below-mentioned (B) component improves, and the sticking property to a polyimide base material can be reduced.

  In addition to the compounds of the general formula (2) and / or the general formula (3), blocking agents such as alcohols, lactams, and oximes can be used in combination so as not to impair the effects of the present invention.

  As the compound of the general formula (2) and / or the general formula (3), a tetracarboxylic acid dihydrate (pyromellitic anhydride) represented by the following formula (14) is preferable.

  The amount of pyromellitic anhydride added is in the range of 10 to 20% with respect to the total amount of isocyanate. When the addition amount is 20% or more, it is difficult to control the viscosity, and workability is deteriorated. If it is less than 10%, sticking to the polyimide film tends to occur after curing.

In the present invention, examples of other resins having an acid anhydride group and / or a carboxyl group that can be used as the component (A) include, for example, the general formula (9), the general formula (10), and the following general formula ( 15) can be mixed and reacted under the same conditions as in the synthesis of (b-1). The resin thus obtained is a urethane resin having a carboxyl group containing a repeating structure represented by the following general formula (16), and the reactivity with an epoxy resin which is a component (B) described later is improved. The sticking property to a polyimide base material can be reduced.
When the urethane resin having a carboxyl group obtained as described above has an isocyanate residue, the isocyanate residue is represented by General Formula (2), General Formula (3), alcohols, lactams, oximes and the like. You may make it react.
Examples of the compound represented by the general formula (15) include dimethylolpropionic acid and dimethylolbutanoic acid.

（式（１５）中、Ｒ^１は、水素原子、炭素数１〜３のアルキル基を示す。）

(In formula (15), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

（式（１６）中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基であり、Ｒ^１は、水素原子、炭素数１〜３のアルキル基であり、Ｘは二価の有機基であり、ｍ及びｎは、それぞれ独立に１〜２０の整数である。）

(In Formula (16), a plurality of R's are each independently an alkylene group having 1 to 18 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X is a divalent group.) It is an organic group, and m and n are each independently an integer of 1 to 20.)

  The number average molecular weight of the resin thus obtained is preferably 15,000 to 50,000, more preferably 20,000 to 45,000, and 25,000 to 40,000. It is particularly preferred that the degree of dispersion at that time is preferably 1.5 to 3.5, more preferably 2.0 to 3.0. When the number average molecular weight is less than 15,000, the cured film and the polyimide film tend to stick to each other. When the number average molecular weight exceeds 50,000, the viscosity of the resin increases, and the inorganic filler and / or Alternatively, it is not preferable because workability such as mixing of organic fillers and screen printing tends to deteriorate.

((B) component: epoxy resin)
In the resin composition of the present invention, various epoxy resins are added to improve thermosetting. Examples of the epoxy resin as the curing agent include bisphenol A type epoxy resin (trade name “Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.) and bisphenol F type epoxy resin (trade name manufactured by Toto Kasei Co., Ltd.). “YDF-170” and the like, phenol novolac type epoxy resin (trade name “Epicoat 152, 154” manufactured by Yuka Shell Epoxy Co., Ltd.); product name “EPPN-201” manufactured by Nippon Kayaku Co., Ltd .; Dow Chemical Company name “DEN-438”, etc.), o-cresol novolac type epoxy resin (Nippon Kayaku Co., Ltd. product name “EOCN-125S, 103S, 104S”, etc.), polyfunctional epoxy resin (oilification) Product name “Epon1031S” manufactured by Shell Epoxy Co., Ltd. Product name “Araldite 01 manufactured by Ciba Specialty Chemicals Co., Ltd.” 3 "; trade name" Denacol EX-611, EX-614, EX-614B, EX-622B, EX-512, EX-521, EX-421, EX-411, EX-321 "manufactured by Nagase Kasei Co., Ltd. Etc.), amine type epoxy resin (trade name “Epicoat 604” manufactured by Yuka Shell Epoxy Co., Ltd.); product name “YH434” manufactured by Tohto Kasei Co., Ltd .; product name “TETRAD-” manufactured by Mitsubishi Gas Chemical Co., Ltd. X ”,“ TERRAD-C ”; trade name“ GAN ”manufactured by Nippon Kayaku Co., Ltd .; trade name“ ELM-120 ”manufactured by Sumitomo Chemical Co., Ltd.), heterocycle-containing epoxy resin (Ciba Specialty) Chemicals Co., Ltd. trade name “Araldite PT810”, etc.), alicyclic epoxy resins (UCL “ERL4234, 4299, 4221, 4206” etc.), etc. In or in combination of two kinds or more may be used. Among these epoxy resins, amine-type epoxy resins having 3 or more epoxy groups in one molecule are particularly preferable in terms of improving solvent resistance, chemical resistance, and moisture resistance.

  These epoxy resins may contain an epoxy compound having only one epoxy group in one molecule. Such an epoxy compound is preferably used in the range of 0 to 20% by weight based on the total amount of the “resin containing an imide bond” as the component (A). Examples of such an epoxy compound include n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, and dibromocresyl glycidyl ether. In addition, alicyclic epoxy compounds such as 3,4-epoxycyclohexyl and methyl (3,4-epoxycyclohexane) carboxylate can be used.

  The amount of these epoxy resins used is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts per 100 parts by weight of “resin having acid anhydride group and / or carboxyl group” used as component (A). Part by weight, more preferably 3 to 40 parts by weight. When the compounding amount of the epoxy resin is less than 1 part by weight, the curability, solvent resistance, chemical resistance, and moisture resistance of the resin composition tend to decrease. When the amount exceeds 50 parts by weight, the heat resistance and viscosity stability are increased. It tends to decrease.

  As the method for adding the epoxy resin, the epoxy resin to be added is used after being dissolved in the same organic solvent as the organic solvent for dissolving the “resin having an acid anhydride group and / or carboxyl group” as the component (A). It may also be added directly.

[(C) component: filler containing hydrotalcite]
The filler used as the component (C) in the present invention contains hydrotalcite. Component (C) used in the resin composition of the present invention is a filler containing hydrotalcite as an essential component. The content of the filler is preferably 1 to 250 parts by weight, more preferably 30 to 200 parts by weight, and more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the component (A). Is particularly preferred. When the content of the component (C) is less than this, the viscosity and thixotropy coefficient of the resin composition paste are lowered, the stringing of the paste is increased, and the flow of the paste after printing is increased. The film thickness also tends to be reduced, and the electrical properties of the cured film tend to be inferior. In addition, when the content of component (C) is higher than this, the viscosity and thixotropy coefficient of the resin composition paste are increased, the transferability of the paste to the substrate is lowered, and voids and pinholes in the printed film are increased. Tend to.

(Particle size of component (C))
Component (C) used in the resin composition of the present invention: The filler is preferably used with a mean particle size of 50 μm or less and a maximum particle size of 100 μm or less. When the average particle diameter exceeds 50 μm, it becomes difficult to obtain a resin composition paste having a thixotropic coefficient of 1.1 or more, which will be described later. When the maximum particle diameter exceeds 100 μm, the appearance and adhesion of the coating film of the resin composition are There is a tendency to become insufficient. The average particle size of the component (C) is more preferably 30 μm or less, further preferably 10 μm or less, and particularly preferably 1 μm or less. Further, the maximum particle size of the component (C) is more preferably 80 μm or less, further preferably 60 μm or less, and particularly preferably 40 μm or less.

(Hydrotalcite)
Hydrotalcite is a condensed hydroxide represented by the following general formula (17).
M ¹ _8-x M ² _x (OH) ₁₆ CO ₃ .nH ₂ O (17)
(In Formula (17), M ¹ represents Mg ²⁺ , Fe ²⁺ , Zn ²⁺ , Ca ²⁺ , Li ²⁺ , Ni ²⁺ , Co ²⁺ , Cu ²⁺ , and M ² represents Al ³⁺ , Fe ³⁺ , Mn ³⁺ . X represents an integer of 2 to 5, and n represents a positive integer.)
Among these, the compound of magnesium and aluminum represented by the following chemical composition formula is particularly preferable, and is commercially available as HT-P (trade name, manufactured by Sakai Chemical Co., Ltd.).
Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O

Hydrotalcite as a filler component added to the resin composition of the present invention has the effect of an antacid and can reduce the thickening of a resin composition containing a resin having an acid anhydride group and / or a carboxyl group There is. Hydrotalcite dissociates carbonate groups to generate carbonate ions (CO ₃ ²⁻ ), and the carbonate ions are contained in the resin composition chloride ions (Cl ⁻ ) and / or sulfate ions (SO 2). ₄ ^-) and it has the effect of substitution. When chloride ions (Cl ⁻ ) and / or sulfate ions (SO ₄ ⁻ ) are present in the cured coating, the insulation reliability is adversely affected, but the insulation reliability can be improved by the substitution action with the carbonate ions. . However, an excessive blending amount is not preferable because it causes problems in printing appearance. Furthermore, by blending hydrotalcite with the resin composition of the present invention, in the wiring board protected by the cured film of the resin composition of the present invention, there is an effect that the black swelling of the electrode after energization can be reduced. can get. Hydrotalcite also has the effect of improving the flame retardancy.

  The hydrotalcite content is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and more preferably 10 to 30 parts by weight with respect to 100 parts by weight of component (A). Is particularly preferred. If the hydrotalcite content is less than 1 part by weight, the effect of reducing the thickening of the resin composition tends to be insufficient, and black swelling of the electrode tends to occur. There is a tendency for the appearance to be affected.

  The content of the hydrotalcite in the component (C) is preferably 10% by mass to 50% by mass, more preferably 10-30% by mass, and 15-25% by mass. Particularly preferred. When the content of hydrotalcite in the component (C) is less than 10% by mass, the effect of reducing the increase in the viscosity of the resin composition becomes insufficient. When the content exceeds 50% by mass, the printed appearance of the resin composition is not satisfactory. The effect will come out.

  As the filler component other than hydrotalcite in the component (C) used in the present invention, an inorganic filler and / or an organic filler can be used. First, the inorganic filler will be described.

As described above, hydrotalcite is a kind of inorganic filler. Examples of inorganic fillers other than hydrotalcite include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), and oxidation. Tantalum (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO · TiO ₂ ), Lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO · Al ₂ O ₃ ), mullite (3Al ₂ O ₃ · 2SiO ₂ ), Cody Eraito _{(2MgO · 2Al 2 O 3 /} 5SiO 2), talc _{(3MgO · 4SiO 2 · H 2} O), aluminum titanate (TiO ₂ -Al ₂ O _3), yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , barium silicate (BaO · 8SiO _2), boron nitride (BN), calcium carbonate (CaCO _3), calcium sulfate (CaSO _4), zinc oxide (ZnO ), Magnesium titanate (MgO · TiO ₂ ), barium sulfate (BaSO ₄ ), organic bentonite, carbon (C), and the like, and one or more of these can also be used.

  Among these inorganic fillers, barium sulfate and talc are preferably used from the viewpoint of improving electrical characteristics (insulation reliability and the like). Moreover, it is preferable to use barium sulfate from a viewpoint of printability and workability.

  One organic filler is preferably heat-resistant resin fine particles having an amide bond, an imide bond, an ester bond or an ether bond. As such a heat-resistant resin, polyimide resin or a precursor thereof, polyamideimide resin or a precursor thereof, or fine particles of polyamide resin are preferably used from the viewpoint of heat resistance and mechanical properties.

The heat resistant resin used as the organic filler can be produced as follows.
First, a polyimide resin which is one of the above heat-resistant resins can be obtained by reacting (c) an aromatic tetracarboxylic dianhydride and (d) an aromatic diamine compound.

  (C) As aromatic tetracarboxylic dianhydride, for example, pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-bis Phenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3 , 4-Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-di Carboxyphenyl Ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3′- Benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1, 4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-terolachlornaphthalene-1, 4,5,8-tetracar Acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methyl Phenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3 , 4-Dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 2,2-bis (3,4-di Carboxyphenyl) hexafluoropropane dianhydride, 2,2-bis {4- (3,4-dicarboxyphenoxy) phenyl} hexafluoropropane dianhydride, 2,2-bis {4- (3,4-dicarboxyphenoxy) phenyl} propane dianhydride, 4,4-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis ( 2-hydroxyhexafluoroisopropyl) benzene bis (trimellitate anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitate anhydride), 1,2- (ethylene) bis (trimellitate anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexa Methylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitate anhydrous) ), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- ( Dodecamemethylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), and the like. May be used.

  In the above (c) aromatic tetracarboxylic dianhydride, a tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride is added according to the purpose, and 50 mol% of the aromatic tetracarboxylic dianhydride is added. It can be used within a range not exceeding. Examples of such tetracarboxylic dianhydrides include ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic Acid dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2 , 3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2, 3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis {exobicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride Thing} sulfone, bishi Rho- (2,2,2) -oct (7) -ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3 -Cyclohexane-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride and the like.

  Next, as the above (d) aromatic diamine compound, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3, , 3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diamino Diphenyl ketone, , 4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2-bis (3,4'-diaminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3,4'-diaminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1, 3-bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 3,3 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,4′- [1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) Phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) Phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, and the like. These may be used in combination.

  In the (d) aromatic diamine compound, a diamine compound other than the aromatic diamine compound can be used in a range not exceeding 50 mol% of the aromatic diamine compound depending on the purpose. Examples of such diamine compounds include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino. Heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetramethylpolysiloxane and the like.

  The (c) aromatic tetracarboxylic dianhydride and the (d) aromatic diamine compound are preferably reacted in an equimolar amount from the viewpoint of the film properties of the resin composition.

  The reaction between (c) the aromatic tetracarboxylic dianhydride and (d) the aromatic diamine compound is carried out in an organic solvent. Examples of the organic solvent in this case include N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3- Nitrogen-containing compounds such as dimethyl-2-imidazolidinone; sulfur compounds such as sulfolane and dimethyl sulfoxide; γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε- Lactones such as caprolactone; dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol (or diethyl, dipropyl, dibutyl) ether, tetraethylene glycol dimethyl (or diethyl, dipro Ethers such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone; butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) Alcohols such as ether and tetraethylene glycol monomethyl (or monoethyl) ether; phenols such as phenol, cresol and xylenol; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate and butyl cellosolve acetate; toluene, xylene, diethylbenzene and cyclohexane Hydrocarbons such as trichloroethane, tetotachloroethane, monochlorobenzene, etc. Rogenated hydrocarbons and the like are used. These organic solvents are used alone or in combination. In consideration of solubility, low hygroscopicity, low temperature curability, environmental safety, etc., it is preferable to use lactones, ethers, ketones and the like.

  The reaction temperature is 80 ° C or lower, preferably 0 to 50 ° C. As the reaction proceeds, the reaction solution gradually thickens. In this case, polyamic acid which is a precursor of the polyimide resin is generated. This polyamic acid may be partially imidized, and this is also included in the polyimide resin precursor.

  The polyimide resin is obtained by dehydrating and ring-closing the reactant (polyamide acid). Dehydration ring closure can be performed by a method of heat treatment at 120 ° C. to 250 ° C. (thermal imidization) or a method of using a dehydrating agent (chemical imidization). In the case of the heat treatment at 120 ° C. to 250 ° C., it is preferable to carry out while removing water generated by the dehydration reaction out of the system. At this time, water may be removed azeotropically using benzene, toluene, xylene or the like.

  In the method of performing dehydration and ring closure using a dehydrating agent, it is preferable to use an acid anhydride such as acetic anhydride, propionic anhydride or benzoic acid, a carbodiimide compound such as dicyclohexylcarbodiimide, or the like as the dehydrating agent. At this time, if necessary, a dehydration catalyst such as pyridine, isoquinoline, trimethylamine, or aminopyridineimidazole may be used. The dehydrating agent or the dehydrating catalyst is preferably used in an amount of 1 to 8 moles per mole of aromatic tetracarboxylic dianhydride.

  The polyamide-imide resin or precursor thereof is trimellitic anhydride or trimellitic anhydride derivative (trimellitic anhydride anhydrous) instead of aromatic tetracarboxylic dianhydride in the production of the polyimide resin or precursor thereof. Trivalent tricarboxylic acid anhydrides or derivatives thereof such as chlorides of the products. Moreover, it can also manufacture using the diisocyanate compound corresponding to the diamine compound in which residues other than an amino group replace with an aromatic diamine compound and another diamine compound. Diisocyanate compounds that can be used include those obtained by reacting the aromatic diamine compound or other diamine compounds with phosgene or thionyl chloride.

  The polyamide resin is produced by reacting an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or phthalic acid, a derivative thereof such as dichloride or acid anhydride, and the above-described aromatic diamine compound or another diamine compound. can do.

  Examples of the heat-resistant resin having an ester bond include a polyester resin. Examples of the polyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic acid, and derivatives such as dichloride and acid anhydride. And an aromatic diol compound such as 1,4-dihydroxybenzene, bisphenol F, bisphenol A, and 4,4'-dihydroxybiphenyl.

  As the polyamideimide resin, a polyamideimide resin obtained by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine compound containing isophthalic acid dihydrazide as an essential component is preferably used. As the aromatic tetracarboxylic dianhydride and the aromatic diamine compound, those described above are used. The molar ratio of isophthalic acid dihydrazide in the aromatic diamine compound is preferably 1 to 100 mol%. If it is less than 1 mol%, the solubility resistance with respect to the modified polyamideimide resin tends to decrease, and if the content of isophthalic acid dihydrazide is large, the moisture resistance of the layer formed by the paste of the resin composition of the present invention tends to decrease. Therefore, 10 to 80 mol% is more preferable, and 20 to 70 mol% is particularly preferably used. This polyamide-imide resin can be obtained in the same manner as the synthesis of the polyimide resin, with respect to the compounding ratio of the aromatic tetracarboxylic dianhydride and the aromatic diamine compound, the organic solvent used, the synthesis method, and the like.

  The polyamideimide resin obtained by reacting trimellitic anhydride and, if necessary, dicarboxylic acid and polyisocyanate is likely to become insoluble in organic solvents when heated, and organic fine particles made of this polyamideimide resin should be used. You can also. About the manufacturing method of this polyamideimide resin, it can manufacture similarly to the manufacturing method of an above described polyamideimide resin.

  Examples of the fine particle method for using the resin as the component (C) as a filler include, for example, a non-aqueous dispersion polymerization method (see, for example, JP-B-60-48531, JP-A-59-230018), Precipitation polymerization method (for example, see JP-A-59-108030 and JP-A-60-221425), a method of mechanically pulverizing powder modified from a resin solution, under high shear while adding the resin solution to a poor catalyst There are a method for making fine particles, a method for obtaining fine particles by drying a spray solution of a resin solution, a method for forming fine particles by precipitation of a resin having a temperature dependency that is soluble in a solvent in a detergent or a resin solution, and the like.

  As described above, the component (C) used in the present invention: the filler (inorganic fine particles and / or organic fine particles containing hydrotalcite) has an average particle size of 50 μm or less and a maximum particle size of 100 μm or less. Is preferably used. When the average particle diameter exceeds 50 μm, it becomes difficult to obtain a paste having a thixotropic coefficient of 1.1 or more, which will be described later, and when the maximum particle diameter exceeds 100 μm, the appearance and adhesion of the coating film of the resin composition are insufficient. Tend to be. The average particle size is more preferably 30 μm or less, further preferably 10 μm or less, particularly preferably 1 μm or less, and the maximum particle size is more preferably 80 μm or less, still more preferably 60 μm or less, particularly preferably 40 μm or less.

(Resin composition)
In the resin composition of the present invention, the resin as component (A) is dissolved in an organic solvent to obtain a resin solution, and the component (C) “inorganic fine particles and / or organic fine particles containing hydrotalcite” are dispersed, Furthermore, the epoxy resin which is (B) component can be added and mixed and manufactured.

  In the resin composition of the present invention, the content of “inorganic fine particles and / or organic fine particles containing hydrotalcite” used as component (C) is 1 to 100 parts by weight of component (A) as described above. The amount is preferably 250 parts by weight, more preferably 30 to 200 parts by weight, and particularly preferably 50 to 100 parts by weight. When the content of the component (C) is less than this, the viscosity and thixotropy coefficient of the resin composition paste are decreased, the stringing of the paste is increased, and the flow of the paste after printing is increased, whereby the resin composition There is also a tendency for the film thickness to be reduced, and the electrical characteristics tend to be inferior. Further, when the content of the component (C) is larger than this, the viscosity and thixotropy coefficient of the resin composition paste are increased, the transferability of the paste to the substrate is lowered, and voids and pinholes in the printed film are formed. There is a tendency to increase.

  (A) As an organic solvent which melt | dissolves resin of a component, as above-mentioned, ether solvents, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether, as a non-nitrogen-containing polar solvent; Sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone and sulfolane; ester solvents such as γ-butyrolactone and cellosolve acetate; ketone solvents such as cyclohexanone and methyl ethyl ketone; aromatic hydrocarbon solvents such as toluene and xylene; These may be used alone or in combination of two or more. Since the solubility varies depending on the resin to be produced, a solvent capable of dissolving the resin is selected and used.

  As a method of dispersing inorganic and / or organic fine particles containing component (C): hydrotalcite in a solution of a thermosetting resin (component (A)), a roll kneading or a mixer usually used in the paint field is used. Any method may be used as long as mixing or the like is applied and sufficient dispersion is performed.

  In the resin composition of the present invention, surfactants such as antifoaming agents and leveling agents, colorants such as dyes and pigments, heat, Stabilizers, antioxidants, flame retardants, and lubricants can also be added.

  The resin composition of the present invention has a viscosity at 25 ° C. of 20 Pa · s to 80 Pa · s, particularly preferably 30 to 50 Pa · s, at 25 ° C. Moreover, it is preferable that a thixotropy coefficient is 1.1 or more. If the viscosity is less than 20 Pa · s, the flow of paste after printing tends to increase and the film thickness tends to be reduced. If the viscosity exceeds 80 Pa · s, the transferability of the paste to the substrate decreases. At the same time, voids and pinholes in the printed film tend to increase. When the thixotropy coefficient is less than 1.1, the stringing of the paste increases, the flow of the paste after printing increases, and the film thickness also tends to be reduced.

  Here, the viscosity of the resin composition is expressed as a viscosity at a rotation speed of 10 rpm measured with a sample amount of 0.2 mL or 0.5 mL using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE80U type). Also, the thixotropy coefficient (TI value) of the paste was applied only to pastes with rotation speeds of 1 rpm and 10 rpm measured with a sample volume of 0.2 mL or 0.5 mL using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., model RE80U) Viscosity is expressed as the ratio η1 / η10 of η1 and η10.

  The present invention can also be suitably used for a flexible wiring board in which the above resin composition is screen-printed on a wiring pattern of a flexible wiring board and then thermally cured to form a cured film to form a protective film. In particular, it is suitable for use as a protective film on the surface of a flexible wiring board in which the wiring pattern portion is tin-plated. The conditions for thermosetting are preferably 80 ° C. to 130 ° C., particularly preferably 90 ° C. to 120 ° C., from the viewpoint of preventing diffusion of the tin plating layer and obtaining low warpage and flexibility suitable as a protective film. It is not limited to this range, For example, it can also be made to harden | cure in the range of 50-200 degreeC, especially 50-140 degreeC. The heating time is 60 to 150 minutes, preferably 80 to 120 minutes from the viewpoint of preventing the diffusion of the plating layer and obtaining low warpage and flexibility suitable as a protective film. It is not limited, It can also be hardened in the range of 1 to 1,000 minutes, for example, 5 to 300 minutes, especially 10 to 150 minutes.

[Coating material]
The film-forming material of the present invention contains the above-described resin composition and is suitably used as a film-forming material for various electrical products and electronic parts in coating methods such as screen printing, dispenser, and spin coating. In particular, it is suitably used for screen printing.

  The film-forming material according to the present invention is suitably used, for example, as an overcoat material for electronic parts such as semiconductor elements and printed circuit boards, a liquid sealing material, an interlayer insulating film, a surface protective film, a solder resist layer, and an adhesive layer. . It can also be used for varnish for enameled wire, impregnated varnish for electrical insulation, cast varnish, mica, glass cloth, varnish for sheet, varnish for MCL laminate, friction material. In addition, since the resin coating is not peeled off from the circuit board or the like, the adhesion between the base material and the resin and the printing workability are excellent, so that a highly reliable electronic component can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

(Synthesis Example 1: Synthesis of polymer resin)
In a 3 liter four-necked flask equipped with a stirrer, a condenser with an oil separator, a nitrogen inlet tube and a thermometer, 61.72 g of γ-butyrolactone, 1,6-hexanediol-based polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd.) , 74.64 g (0.37 mol) of trade name “Placcel CD-220”, 125.14 g (0.46 mol) of 4,4′-diphenylmethane diisocyanate, 58.4 g (0.34 mol) of toluene diisocyanate, The temperature was raised to 150 ° C. and reacted at 150 ° C. for 4 hours.

  Next, 88.4 g (0.46 mol) of trimellitic anhydride was added to the reaction product and reacted at 70 ° C. for 3 hours. Subsequently, 6.76 g (0.027 mol) of 4,4′-diphenylmethane diisocyanate and 0.0034 g (0.00002 mol) of toluene diisocyanate were charged again and reacted at 120 ° C. for 1 hour and at 180 ° C. for 3 hours. After the reaction, 341.6 g of butyl carbitol acetate was charged and cooled, and 0.02 g (0.0001 mol) of pyromellitic anhydride was further charged and reacted at 120 ° C. for 3 hours to give a resin having a number average molecular weight of 38,000 ( Polycarbonate-modified polyamideimide resin (component (A) of the present invention) was obtained. The number average molecular weight can be adjusted by collecting a small amount of the reaction solution for each reaction time and observing the rate of change in viscosity using a Gardner bubble viscometer. The obtained resin was diluted with butyl carbitol acetate to obtain a polycarbonate-modified polyamideimide resin solution having a nonvolatile content of 50% by weight.

Example 1
In the polycarbonate-modified polyamideimide resin solution having a number average molecular weight of 38,000 obtained in the above (Synthesis Example 1), 1 part by weight of a solvent treatment solution and 100 parts by weight of an antifoaming agent with respect to 100 parts by weight of the resin content of the resin solution (BIC Chemie, trade name “BYK-051”) 0.3 parts by weight, leveling agent (Bick Chemie, trade name “BYK-354”) 0.75 parts by weight were blended and stirred at 20 ° C. for 10 minutes. . Furthermore, 66.5 parts by weight of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., trade name “B-31”), 13.5 parts by weight of talc (manufactured by Nippon Talc Co., Ltd., trade name “ST-2000”) and Hydrotalcite (manufactured by Sakai Chemical Industry Co., Ltd., trade name “HT-P”) 10 parts by weight previously dispersed in a bead mill (component (C) of the present invention) is blended, and γ-butyrolactone or the like is added as necessary. A solvent was added and the mixture was stirred at 50 ° C. for 1 hour. Further, 10 parts by weight of an amine type epoxy resin (manufactured by Tohto Kasei Co., Ltd., trade name “YH-434L”) was added as a component (B) of the present invention, and the mixture was heated at 20 ° C. The mixture was stirred for 1 hour to obtain a polycarbonate-modified polyamideimide resin composition.

(Example 2)
Except that hydrotalcite was changed to 20 parts by weight in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

(Example 3)
Except that hydrotalcite was changed to 30 parts by weight in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

Example 4
Except that hydrotalcite was changed to 50 parts by weight in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

(Comparative Example 1)
The resin blended in Synthesis Example 1 was not the one obtained by reacting the terminal isocyanate with pyromellitic anhydride, but the one reacted with oxime (resin having no acid anhydride group and / or carboxyl group), Example 1 Exactly the same operation was performed to obtain a polycarbonate-modified polyamideimide resin composition.

(Comparative Example 2)
Except that hydrotalcite was not blended in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

  Each polycarbonate-modified polyamideimide resin composition obtained in the above Examples and Comparative Examples, and adhesion characteristics, printed appearance, and black blistering reduction properties of the cured film of these polyamideimide resin compositions to the polyimide film are described below. The results are shown in Table 1.

(Storage stability)
The viscosity of the produced polycarbonate-modified polyamideimide resin composition was measured with a rotary viscometer, and the viscosity was measured in the same manner 48 hours later, and the viscosity increase rate from the time of production was calculated. The smaller the value, the better the storage stability.

(Print appearance)
The obtained polycarbonate-modified polyamideimide resin composition is printed on a 35 μm copper foil using a printing machine (trade name “LS-34GX” manufactured by Neurong Co., Ltd.) and a mesh plate (150 mesh manufactured by Murakami Co., Ltd.). A 30 mm square was printed at a speed of 100 mm / sec, and the appearance after the printing (foam marks, aggregates, etc.) was observed with an optical microscope of 100 magnification.
○ where no defects such as bubble marks and aggregates were observed, △ where defects such as bubble marks and aggregates were observed in a part of the printed part, and bubbles marks and aggregates over the entire printed part The case where defects such as were observed was evaluated as x.

(Check for black swelling of the electrode after energization)
The resulting polycarbonate-modified polyamideimide resin composition was covered with a printing machine (manufactured by Neurong Co., Ltd.) so as to cover a copper electrode tin-plated in a comb shape with a line width of 15 μm and a space width of 15 μm. : LS-34GX) and a mesh plate (150 mesh manufactured by Murakami Co., Ltd.), printed at a printing speed of 100 mm / sec, and cured by heating in an air atmosphere at 120 ° C. for 60 minutes to form a cured coating of a polycarbonate-modified polyamideimide resin A polyimide substrate comb-type electrode was obtained. The resulting polyimide base comb-shaped electrode with a cured polycarbonate-modified polyamideimide resin film was subjected to a continuous resistance measuring machine (product name “Ion Migration Tester MIG-8600” manufactured by IMV Corporation) and an unsaturated pressure cooker (Hirayama Corporation). Using a product name “HAST PC-422R8D” manufactured by Seisakusho Co., Ltd.) and energizing under conditions of a temperature of 120 ° C., a humidity of 85%, an applied voltage of 60 V, and an applied time of 100 hours. Were observed with an optical microscope.
Evaluation was made with a circle having no black blisters as ◯, a sample with slight black blisters as Δ, and a sample with a large amount of black blisters as x.

(Adhesiveness)
A test piece obtained by curing the polycarbonate-modified polyamideimide resin composition after printing in an air environment at 120 ° C. for 60 minutes, a polyimide film, and a copper plate are overlaid, loaded with a weight of 2 kg, and 90 μm in a pot plate. The sticking property between the test piece and the polyimide film after heating at ˜120 ° C. for 30 seconds was measured. Evaluation was based on the temperature at which sticking began to occur.
It is preferable that the temperature at which sticking begins to occur is higher.

From the above results, the following can be confirmed.
That is, from the comparison between Comparative Example 1 and other examples, when the terminal isocyanate is modified with pyromellitic anhydride, the reaction with the amine type epoxy resin is promoted, and the sticking with the cured polyimide film is reduced. I understand that.
Moreover, in Examples 2-4 and Comparative Example 2, thickening can be reduced by increasing the blending amount of hydrotalcite. Furthermore, the black swelling of the electrode after electricity supply can be reduced by mix | blending a hydrotalcite. However, an excessive blending amount caused a problem in printing appearance.

  As described above, the resin composition and the film-forming material according to the present invention are suitably used for coating methods such as screen printing, dispenser, and spin coating as film-forming materials for various electric products and electronic parts. Moreover, since it is hard to stick with the polyimide film after hardening, it is useful in terms of workability and cost, such as eliminating the spacer between the polyimide film and the cured film.

Claims (7)

  (A) Component: Resin having an acid anhydride group and / or carboxyl group, (B) component: epoxy resin, and (C) component: filler containing hydrotalcite Composition.   The resin composition according to claim 1, wherein the component (A) has a polycarbonate skeleton. The component (A) is represented by the following general formula (1)

(In the formula (1), a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, and a plurality of X's each independently represents an alkylene group or arylene group having 1 to 18 carbon atoms, The resin composition according to claim 1, wherein m and n each independently include a structural unit represented by an integer of 1 to 20.   The component (A) is an isocyanate residue of at least one resin selected from a polyimide resin having a polycarbonate skeleton, a polyamideimide resin, and a polyamide resin, and a trivalent or higher polycarboxylic acid having an acid anhydride group or its The resin composition according to claim 1, which is a resin obtained by reacting with a derivative.   The content of the component (C) is 10 to 50 parts by weight with respect to 100 parts by weight of the component (A), and the content of hydrotalcite in the component (C) is 10% by mass to 50%. It is the mass%, The resin composition of Claim 1 characterized by the above-mentioned.   The resin composition according to any one of claims 1 to 5, wherein the resin composition is used for a protective film of a flexible printed board in which a copper foil is laminated on a polyimide base material.   A film-forming material comprising the resin composition according to claim 1.