JPWO2008047866A1 - Resin composition and film-forming material containing the same - Google Patents

Abstract

Provided are a resin composition excellent in reliability even under a high temperature and humidity condition, and a film forming material containing the resin composition. The resin composition includes a resin, inorganic fine particles, and a triazine thiol derivative. As a triazine thiol derivative, the following general formula (1): [Chemical Formula 1] (wherein R1 represents —SH and —N (R2R3). 6 alkyl group or an aryl group which may have a substituent.) Is preferably used. The triazine thiol derivative is preferably used in the range of 0.1% by weight to 5.0% by weight with respect to the total solid content of the resin composition.

Description

  The present invention relates to a resin composition suitable for use in coating methods such as a screen printer, a dispenser, and a spin coater, and a film forming material containing the resin composition.

  In the field of electronic components, polyimide resin, polyamideimide resin, and polyamide resin are used in place of epoxy resin as a resin that excels in heat resistance, electrical properties, and moisture resistance because of the reduction in size, thickness, and speed. Yes. These resins have a rigid resin structure. Therefore, when used for forming a thin film on the surface of a substrate, the substrate after the thin film cures greatly, and the formed cured film lacks flexibility and has poor flexibility. There is a problem. Thus, in order to improve the low warpage of the substrate and the flexibility of the cured thin film by forming a cured thin film, a polyamideimide resin has been proposed in which the resin is modified to make it flexible and have a low elastic modulus (for example, patents). (Disclosed in Literature 1, Patent Literature 2, and Patent Literature 3). Fillers are added to these resins to improve heat resistance and moisture resistance.

In recent years, electronic devices have become smaller, thinner, and faster, and FPC (Flexible Printed Circuit), TAB (Tape)
There are technologies such as Automated Bonding: a mounting technology for bonding a semiconductor chip and a circuit board through a tape-like film) and COF (Chip On Film: a driver IC mounted on a film-like printed wiring board). As seen in these technologies, the wiring pitch of the flexible wiring board has been further refined, and the wiring thickness has been made thinner accordingly.

  Conventionally, in order to maintain the insulation reliability between the wirings, an insulating thermosetting resin paste is usually applied and cured on the wirings to form an insulating protective film. However, when the fine pitch wiring having a pitch of 40 μm or less is used in order to realize the above-described high definition, even if the insulating protective film is formed using the conventional thermosetting resin paste, the high temperature and humidity resistance of the insulating protective film is When the voltage is applied to the wiring under high temperature and high humidity conditions, the insulation between the wirings deteriorates, and there is a problem that the insulation reliability cannot be maintained for a long time.

JP 62-106960 A Japanese Patent Laid-Open No. 08-012763 JP 07-196798 A

  The present invention has been made in view of the above-described conventional problems, and an object thereof is to provide a resin composition excellent in insulation reliability even under high temperature and humidity conditions, and a film forming material including the resin composition.

  In order to solve the above-mentioned problems, the resin composition according to the present invention includes a resin (A), inorganic fine particles (B), and a triazine thiol derivative (C).

  The triazine thiol derivative (C) is preferably a compound represented by the following general formula (1).

（式中、Ｒ^１は、−ＳＨ及び−Ｎ（Ｒ^２Ｒ^３）を示す。Ｒ^２及びＲ^３はそれぞれ独立に水素原子、炭素数１〜６のアルキル基又は置換基を有していてもよいアリール基を示す。）

(In the formula, R ¹ represents —SH and —N (R ² R ³ ). R ² and R ³ each independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituent. Represents a good aryl group.)

  Further, the content of the triazine thiol derivative (C) is preferably 0.1% by weight to 5% by weight with respect to the total solid content of the resin composition.

  In the resin composition of the present invention, the resin (A) preferably contains a polycarbonate skeleton.

（式中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基であり、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 the resin composition of the present invention, the resin (A) preferably includes a polyurethane structure represented by the following general formula (2).

(In the formula, 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). .)

  The resin (A) is preferably selected from the group consisting of a polyimide resin, a polyamideimide resin, a polyamide resin, a modified polyimide resin, a modified polyamideimide resin, and a modified polyamide resin.

  Moreover, it is preferable that the resin composition of this invention contains a solvent (D) further.

  Moreover, it is preferable that the resin composition of this invention contains an epoxy resin (E) further.

  Moreover, it is preferable that the resin composition of this invention is a resin composition for the film formation of a flexible wiring board.

  The film-forming material of the present invention is characterized by containing the resin composition of the present invention.

  The resin composition and film-forming material of the present invention have excellent printability, workability and insulation reliability, and can form a film with high temperature and humidity resistance and good surface wettability. Overcoat materials for electronic parts, liquid encapsulants, varnishes for enamel wires, impregnated varnishes for electrical insulation, varnishes for laminated plates, varnishes for friction materials, printed circuit board fields, interlayer insulation films, surface protective films, solder resist films In addition, it can be suitably used for forming various coatings on electronic parts such as adhesive layers and semiconductor elements. It is particularly useful as a protective film for flexible wiring boards for COF applications.

(Resin (A))
In order to improve the heat resistance, electrical properties, moisture resistance, solvent resistance and chemical resistance of the cured film formed from the resin composition, it is necessary to introduce a component capable of improving heat resistance into the main chain of the resin. As the resin (A), for example, a urethane resin, a polyimide resin, a polyamideimide resin, a polyamide resin, or a resin having these skeletons is preferable. Among these, a resin having a polycarbonate skeleton and a urethane bond is preferable from the viewpoint of flexibility and low elastic modulus. Moreover, resin containing an imide bond is more preferable from the viewpoint of increasing heat resistance.

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

  In the present invention, the “resin containing an imide bond” that can be used as the component (A) is usually a component (a): a trivalent polycarboxylic acid having an acid anhydride group and a derivative thereof, and an acid. It can be obtained by reacting at least one compound selected from tetravalent polycarboxylic acids having an anhydride group with component (b): an isocyanate compound or an amine compound.

  The “trivalent polycarboxylic acid having an acid anhydride group and its derivative” used as the component (a) is not particularly limited, and examples thereof include the following formulas (3) and (4):

（式（３）及び（４）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 (3) and (4), 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-)
The compound shown by these can be used.

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

  Although the “tetravalent polycarboxylic acid having an acid anhydride group” used as the component (a) is not particularly limited, for example, the following formula (5):

（式（５）中、Ｙ²は、下記式（６）：

(In formula (5), Y ² represents the following formula (6):

で示される複数の基から選ばれる一種である）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 (1) selected from a plurality of groups represented by (2). 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 (7):

（式（７）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「ポリカーボネート骨格及びウレタン結合を有する化合物」を用いることができる。

(In Formula (7), 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 1 to 20) It is possible to use “a compound having a polycarbonate skeleton and a urethane bond”.

  The “compound having a polycarbonate skeleton and a urethane bond” represented by the above formula (7) is represented by the following formula (8):

（式（８）中、Ｒは、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（９）：
ＯＣＮ−Ｘ−ＮＣＯ （９）
（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 formula (8), R is an alkylene group having 1 to 18 carbon atoms, and m is an integer of 1 to 20), and the following formula (9):
OCN-X-NCO (9)
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 above formula (9) include 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, hydrogenated diphenylmethane-4,4'-diyl group, diphenylsulfone-4,4'-diyl group are also preferred.

  Examples of carbonate diols represented by the above formula (8) 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 (9) 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; Diphenylmethane-4,4'-diisocyanate; diphenylsulfone-4,4'-diisocyanate; tolylene- diphenylmethane-4,4'-diisocyanate; diphenyl ether-4,4'-diisocyanate; 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 and the like. 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.

  In addition, the diisocyanates represented by the above formula (9) include, within the scope of the object of the present invention, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate. , Transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, lysine diisocyanate, or other aliphatic or alicyclic isocyanates, or trifunctional or higher functional polyisocyanates can be used.

  Diisocyanates represented by the above formula (9) 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 blending ratio of the carbonate diols represented by the above formula (8) and the diisocyanates represented by the above formula (9) 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 (8) and the diisocyanates represented by the formula (9) 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 formula (9), trivalent or higher polyisocyanates, and the like. It is done. These can be used alone or in combination of two or more. A 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 in this range, it is possible to obtain both good low warpage and adhesion, and film properties such as good heat resistance.

  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 above 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.

  In the case where the compound represented by the formula (3) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (10):

（式（１０）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 (10), 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) A polyamideimide resin having a repeating unit represented by the following formula can be obtained.

  When the compound represented by the formula (4) 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 (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) And Y ¹ is —CH ₂ —, —CO—, —SO ₂ —, or —O—).

  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、Ｙ²は、前記式（６）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 (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) Y ² is a group selected from a plurality of groups represented by the formula (6)), and a polyimide resin having a repeating unit represented by the formula (6) can be obtained.

（式中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基であり、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。）As described above, the resin (A) as the component (A) preferably includes a polyurethane structure represented by the following general formula (2) from the viewpoints of flexibility and low elastic modulus.

(In the formula, 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). .)

  In the present invention, component (a) in the method for producing “resin containing an imide bond” used as component (A): a trivalent polycarboxylic acid having an acid anhydride group and its derivative, and an acid anhydride group The reaction between one or more compounds selected from the tetravalent polycarboxylic acids possessed and component (b): an isocyanate compound or an amine compound is liberated in the presence of an organic solvent, preferably a non-nitrogen-containing polar solvent. It can be carried out by heat condensation while removing the generated carbon dioxide gas 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 to 5.0 times (weight ratio) of resin 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.

  In addition, after completion of the synthesis, the isocyanate group at the resin terminal can be blocked with a blocking agent such as alcohols, lactams, oximes, carboxylic acids, and acid anhydrides. In addition, it is preferable to use a thermosetting resin as (A) component.

  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. If the number average molecular weight is less than 15,000, the film properties after tin plating tend to deteriorate. If the number average molecular weight exceeds 50,000, it is difficult to dissolve in a non-nitrogen-containing polar solvent, and during synthesis, Easy to insolubilize. In addition, workability tends to be inferior.

The resin of component (A) used in the resin composition of the present invention may be a mixture of two or more resins having different molecular weights as long as the number average molecular weight measured by the GPC method is within the above range.
Of the resins having different number average molecular weights, the minimum molecular weight is preferably 15,000 or more in terms of number average molecular weight. When the number average molecular weight is less than 15,000, the moisture resistance and heat resistance tend to decrease, which is not preferable. On the other hand, among resins having different number average molecular weights, the maximum molecular weight is preferably less than 50,000 in number average molecular weight. When the number average molecular weight exceeds 50,000, the viscosity of the resin increases, and the workability such as mixing of the inorganic filler and / or organic filler and screen printing tends to decrease.

  The mixing ratio when mixing two or more resins having different number average molecular weights used in the present invention can be mixed without particular limitation as long as the number average molecular weight measured by the GPC method is within the above range. Further, the concentration of the resin solution can be selected without limitation.

  The content of the resin (A) in the resin composition of the present invention is 50 to 99 parts by weight in 100 parts by weight of the total solid content of the resin composition excluding (B) inorganic fine particles of the present invention. More preferably, it is 60-98 weight part, More preferably, it is 70-95 weight part. When the content of the resin (A) is less than 50 parts by weight, heat resistance and reliability tend to decrease, and when it exceeds 99 parts by weight, curability and the like tend to decrease.

(Inorganic particles (B))
The inorganic fine particles (B) to be blended in the resin composition of the present invention are not particularly limited as long as they are dispersed in the resin (A) solution to form a paste. Examples of such inorganic fine particles include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and 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} ), cordierite _{(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} - and rO _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), sulfuric acid Barium (BaSO ₄ ), organic bentonite, carbon (C), hydrotalcite, and the like can be used, and one or more of these can also be used. Among these, silica is preferable from the viewpoint of suppressing the flow of paste after printing, and barium sulfate is preferable from the viewpoint of improving the insulation reliability of the cured film.

  As the inorganic particles (B) to be blended in the resin composition of the present invention, those having an average particle size of 50 μm or less and a maximum particle size of 100 μm or less are 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.

  The content of the inorganic particles used as the component (B) is preferably 10 to 200 parts by weight, more preferably 20 to 180 parts by weight, and more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the component (A). Part is particularly preferable, and 50 to 120 parts by weight is most preferable. If the content of component (B) is less than 10 parts by weight, the viscosity and thixotropy coefficient of the paste will be low, the stringing of the paste will increase, the paste will flow out after printing, and the film thickness will also tend to be thin. There is a tendency that the state and electrical characteristics of the coating end after tin plating are inferior. On the other hand, when the content of component (B) exceeds 200 parts by weight, the viscosity and thixotropy coefficient of the paste increase, transferability of the paste to the substrate decreases, and voids and pinholes in the printed film increase. Tend.

  As a method of dispersing the inorganic particles (B) in the resin solution, roll dispersion, mixer mixing, and the like that are usually performed in the paint field are applied, and the dispersion method is particularly suitable as long as the dispersion is performed sufficiently. It is not limited.

(Triazinethiol derivative (C))
Although there is no restriction | limiting in particular as a triazine thiol type derivative (C) mix | blended with the resin composition of this invention, It is preferable to use the compound represented by following General formula (1).

（式中、Ｒ^１は、−ＳＨ及び−Ｎ（Ｒ^２Ｒ^３）を示す。Ｒ^２及びＲ^３はそれぞれ独立に水素原子、炭素数１〜６のアルキル基又は置換基を有していてもよいアリール基を示す。）

(In the formula, R ¹ represents —SH and —N (R ² R ³ ). R ² and R ³ each independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituent. Represents a good aryl group.)

  Examples of the compound represented by the general formula (1) include 2,4,6-trimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4, Examples include 6-dimercapto-s-triazine. Commercially available products of these compounds include “DISNET F” (trade name: 2,4,6-trimercapto-s-triazine) and “DISNET DB” (trade name: 2-dibutylamino) manufactured by Sankyo Kasei Co., Ltd. -4,6-dimercapto-s-triazine) and "disnet AF" (trade name: 2-anilino-4,6-dimercapto-s-triazine).

  The above triazine thiol derivative may be used alone, but in some cases, several kinds may be used in combination, and the content is preferably set to 0. 0 with respect to the resin solid content excluding (B) inorganic fine particles of the resin composition. The amount is 1 to 5% by weight, and more preferably 0.5 to 3% by weight is added. When the content is less than 0.1% by weight, the effect is hardly exhibited, and when the content is more than 5% by weight, printability and workability are deteriorated.

((D) component: solvent)
In the resin composition of the present invention, various solvents can be used as the component (D). As the solvent, as a non-nitrogen-containing polar solvent, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol, diethyl ether and triethylene glycol diethyl ether; sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone and sulfolane; γ- Ester solvents such as butyrolactone, 2- (2-n-butoxyethoxy) ethyl acetate and cellosolve acetate; ketone solvents such as cyclohexanone and methyl ethyl ketone; aromatic hydrocarbon solvents such as toluene and xylene; monoterpenes such as limonene A solvent etc. are mentioned, These can be used individually or in combination of 2 or more types.
Of the above solvents, γ-butyrolactone is preferably used from the viewpoint of printability.

(Other resin components)
In the resin composition of the present invention, various epoxy resins can be optionally added as the component (E) in order 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" etc.), phenol novolac type epoxy resin (trade name "Epicoat 152,154" manufactured by Yuka Shell Epoxy Co., Ltd.); trade 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” used 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 content of these epoxy resins is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, and further preferably 3 to 40 parts by weight with respect to 100 parts by weight of the “resin” used as the component (A). Is done. If the content of the epoxy resin is less than 1 part by weight, the curability, solvent resistance, chemical resistance, and moisture resistance tend to decrease, and if it exceeds 50 parts by weight, the heat resistance and viscosity stability tend to decrease. is there.

  As the method for adding the epoxy resin, the epoxy resin to be added may be added after being dissolved in the same organic solvent as the organic solvent for dissolving the “resin” used as the component (A), or directly added. Also good.

(Other additives)
As the antifoaming agent or leveling agent to be added to the resin composition of the present invention, “KS-602A”, “KS-603”, “KS-608”, “FA600” (above, manufactured by Shin-Etsu Chemical Co., Ltd .: commodity Name), “BYK-A506”, “BYK-A525”, “BYK-A530”, “BYK-A500”, “BYK-A500”, “BYK-A501”, “BYK-A515”, “BYK-A555” , “Byketol-OK” (above, manufactured by Big Chemie Japan Co., Ltd .: trade name), “ARUFON UP-1000” (made by Toa Gosei Co., Ltd .: trade name), etc. are preferably used. Not what you want. The antifoaming agent, leveling agent and the like may be used alone, but in some cases, several types may be used in combination. The content is preferably 0.05% by weight to 1% with respect to the solid content of the resin composition. The weight percentage is preferably 0.05% by weight to 0.5% by weight. When the content is 0.05% by weight or less, the defoaming property and film forming property are lowered. When the content exceeds 1% by weight, the defoaming property is improved, but the shape retaining property is lowered.

  The resin composition of the present invention is suitably used as various film forming materials. In order to improve the workability at the time of coating and the film characteristics before and after the film formation, this resin composition has colorants such as epoxy resin, phenol resin, dye or pigment, heat stabilizer, antioxidant, flame retardant. A lubricant or the like can also be added.

(Film forming material)
The resin composition according to the present invention is suitably used as a film forming resin composition or a film forming material. Examples of film forming materials include electronic component overcoat materials, liquid encapsulants, enameled wire varnishes, electrical insulation impregnating varnishes, cast varnishes, mica, and glass cloth varnishes, It can be used for varnishes for MCL laminates, varnishes for friction materials, interlayer insulating films, surface protective films, solder resist layers, adhesive layers and the like in the printed circuit board field. The film forming resin composition or film forming material can also be used for electronic parts such as semiconductor elements, and in particular, a flexible wiring board for COF in which the wiring pattern portion is tin-plated before forming the resin composition. It is useful as a protective film.

  When the resin composition according to the present invention is used for a protective film of a COF-use flexible wiring board whose wiring pattern portion is tin-plated, the heating temperature condition of thermosetting prevents diffusion of the tin-plated layer and serves as a protective film. From the viewpoint of obtaining suitable warpage and flexibility, the temperature is preferably 80 to 130 ° C, and particularly preferably 90 to 120 ° C. The heating time for thermosetting is preferably 60 to 150 minutes, and preferably 80 to 120 minutes from the viewpoint of preventing the diffusion of the tin plating layer and obtaining warpage and flexibility suitable as a protective film. Is particularly preferred.

  In the present invention, the film-forming material may be added with other components as necessary to the resin composition of the present invention itself or to the resin composition of the present invention.

  The film-forming material containing the resin composition of the present invention preferably has appropriate wettability. When the wettability is defined by the contact angle of the liquid sealing material with respect to the cured coating film of the film forming material of the present invention, the contact angle with the liquid sealing material dropped on the cured coating film is set to 35 ° or less. It is preferable. When the contact angle with the liquid encapsulant is larger than 35 °, the liquid encapsulant becomes insufficiently spread and, for example, when used for semiconductor coating, the peripheral portion of the IC connection portion can be sufficiently covered. become unable. The contact angle with the sealing material can be measured with a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.).

  Hereinafter, the present invention will be described in detail with reference to examples. The examples shown below are examples for suitably explaining the present invention, and do not limit the present invention at all.

Example 1
To a 5 liter four-necked flask equipped with a stirrer, a cooling pipe with an oil / water separator, a nitrogen introduction pipe and a thermometer, a 1,6-hexanediol-based polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd., trade name “PLACCEL CD-”) 220 ”), 1000.0 g (0.50 mol), 4,4′-diphenylmethane diisocyanate 250.27 g (1.00 mol), and γ-butyrolactone 833.51 g, and the temperature was raised to 140 ° C. The reaction was carried out at 140 ° C. for 5 hours to obtain diisocyanate.

  Subsequently, 288.20 g (1.50 mol) of trimellitic anhydride, 125.14 g (0.50 mol) of 4,4′-diphenylmethane diisocyanate, and 1361.14 g of γ-butyrolactone were added to the reaction solution (diisocyanate). Was heated to 160 ° C. and reacted for 6 hours to obtain a resin (resin (A)) having a number average molecular weight of 18,000. The obtained resin was diluted with γ-butyrolactone to obtain a resin solution having a viscosity of 160 Pa · s and a nonvolatile content of 52% by weight.

  10 parts by weight of amine type epoxy resin (trade name “YH-434”, product name “YH-434”, epoxy equivalent of about 120, 4 epoxy groups / molecule) manufactured by Toto Kasei Co., Ltd.) with respect to 100 parts by weight of the resin content of the obtained resin solution. Then, γ-butyrolactone was added to obtain a resin solution having a viscosity of 100 Pa · s and a nonvolatile content of 52% by weight. Into 2373 g (resin solid content 1234 g) of the obtained resin solution, 61.7 g of silica particles (manufactured by Nippon Aerosil Co., Ltd., trade name “Aerosil 380”, average particle diameter of 0.2 μm or less) as inorganic particles (B), and Add 185.3 g of barium sulfate particles (manufactured by Sakai Chemical Industry Co., Ltd., trade name “B-30, average particle size 0.3 μm”), first kneaded roughly, and then kneaded three times using three high-speed rolls. This kneading was repeated to obtain a resin composition in which silica fine particles were uniformly dispersed.

  After adding 1.234 g of “Disnet DB” (trade name, manufactured by Sankyo Kasei Co., Ltd.) as the triazine thiol derivative (C) to the resin composition obtained above, the mixture was stirred for 3 minutes with a self-revolving stirrer, A resin composition of the present invention was obtained.

(Example 2)
Except that the content of “disnet DB” (triazinethiol derivative (C)) in Example 1 was changed to 12.34 g, the same operation as in Example 1 was performed to obtain the resin composition of the present invention. .

(Example 3)
Except that the content of “disnet DB” (triazinethiol derivative (C)) in Example 1 was changed to 61.7 g, the same operation as in Example 1 was performed to obtain the resin composition of the present invention.

Example 4
Except for adding 1.234 g of “disnet F” (trade name, manufactured by Sankyo Kasei Co., Ltd.) instead of “disnet DB” as the triazine thiol derivative (C), the same operation as in Example 1 was performed, A resin composition of the present invention was obtained.

(Example 5)
A resin composition was obtained in exactly the same manner as in Example 1, except that the content of “Gisnet F” in Example 4 was changed to 12.34 g.

(Example 6)
Except that the content of “disnet F” in Example 4 was changed to 61.7 g, the same operation as in Example 1 was performed to obtain a resin composition.

(Example 7)
A resin composition was obtained in the same manner as in Example 1, except that 3.8 g of dysnet DB was added when 12.34 g of dysnet F was added.

(Example 8)
A resin composition was obtained in the same manner as in Example 1, except that 12.34 g of dysnet F was added and 19.7 g of dysnet DB was added.

(Comparative Example 1)
A resin composition was obtained in the same manner as in Example 1 except that “Disnet DB” (triazinethiol derivative (C)) was not used in Example 1.

  The characteristics of each resin composition obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in (Table 1) and (Table 2).

(1) Printability Each resin composition obtained on a 35 μm copper foil was printed with a printing machine (trade name “LZ-045” manufactured by Neurong Co., Ltd.) and a mesh plate (150 mesh manufactured by Murakami Co., Ltd.) Was printed at 10 mm square at a printing speed of 100 mm / sec, dried at 90 ° C. for 30 minutes in an air atmosphere, and then heated and cured at 120 ° C. for 60 minutes in an air atmosphere to form a resin film. For each resin film, the surface state was observed with a universal projector (Nikon Corporation magnification: 50 times). If there was no irregularities on the surface, it was marked as ◯, and if irregularities were seen on the surface, it was marked as x. evaluated.

(2) Insulation reliability test In a copper wiring pattern of L / S = 15 μm / 15 μm, the film thickness after curing of the obtained resin composition on the sputtering substrate tin-plated on the copper wiring is 10 μm. Printing was performed and thermosetting was performed at 120 ° C. for 60 minutes. The obtained resin film was placed in an environment of a temperature of 120 ° C. and a humidity of 85%, a voltage of DC 60 V was continuously applied, and the retention of insulation resistance after 100 hours was evaluated. A sample having an insulation resistance of 10 ⁷ Ω or more after 100 hours was evaluated as ◯, and a sample having an insulation resistance of less than 10 ⁷ Ω was evaluated as x.

(3) Wettability with the sealing material (contact angle)
Each obtained resin composition is applied onto a rough surface of an electrolytic copper foil having a thickness of 35 μm or a polyimide film having a thickness of 50 μm, dried at 90 ° C. for 15 minutes, and then heated at 120 ° C. for 60 minutes in an air atmosphere. Then, 10 μL of an epoxy-based sealing material (manufactured by Hitachi Chemical Co., Ltd., trade name “CEL-C-5020”) is dropped onto the cured coating film (thickness 20 to 30 μm) of each resin composition obtained. Then, the contact angle with the cured coating film was measured using a contact angle measuring device (manufactured by Kyowa Interface Science). Moreover, the interface of a sealing material and a cured coating film was observed using the universal projector (Nikon Corporation magnification 50 times). The observation criteria are as follows.
○: No boundary between the sealing material and the cured film ×: There is a boundary between the sealing material and the cured film

From the above results, the following can be understood.
Examples 1 to 8 were installed in an environment of a temperature of 120 ° C. and a humidity of 85%, and maintained insulation resistance even when a voltage of DC 60 V was continuously applied for 100 hours. Therefore, it was found that the resin composition of the present invention and the resin coating thereof show a stable insulation resistance for 100 hours or more even in a high temperature and high humidity environment such as a temperature of 120 ° C., a humidity of 85%, and a voltage of 60V. . Moreover, the contact angle with the sealing material was small, and the wettability was improved.
On the other hand, in Comparative Example 1, the insulation resistance decreased in 50 hours.

  The resin composition for screen printing and the film-forming material of the present invention have the above-mentioned excellent characteristics, such as an overcoat material for electronic parts, a liquid sealing material, an varnish for enameled wire varnish for electrical insulation, and a varnish for laminates. It is suitably used for electronic parts such as varnishes for friction materials, interlayer insulating films in the field of printed circuit boards, surface protective films, solder resist films, adhesive layers, and semiconductor elements.

Claims (10)

  A resin composition comprising a resin (A), inorganic fine particles (B), and a triazine thiol derivative (C). The resin composition according to claim 1, wherein the triazine thiol derivative (C) is represented by the following general formula (1):

(In the formula, R ¹ represents —SH and —N (R ² R ³ ). R ² and R ³ each independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituent. A resin composition characterized by being a compound represented by:   2. The resin composition according to claim 1, wherein the content of the triazine thiol derivative (C) is 0.1% to 5% by weight with respect to the total solid content of the resin component. Composition.   The resin composition according to claim 1, wherein the resin (A) includes a polycarbonate skeleton. The resin composition of Claim 1 WHEREIN: The said resin (A) contains the polyurethane structure represented by following General formula (2), The resin composition characterized by the above-mentioned.

(In the formula, 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). .)   The resin composition according to claim 1, wherein the resin (A) is composed of a polyimide resin, a polyamideimide resin, a polyamide resin, a modified polyimide resin, a modified polyamideimide resin, and a modified polyamide resin. The resin composition characterized by being selected from these.   The resin composition according to claim 1, further comprising a solvent (D).   The resin composition according to claim 1, further comprising an epoxy resin (E).   The resin composition according to claim 1 is a resin composition for forming a film on a flexible wiring board.   A film-forming material comprising the resin composition according to claim 1.