JP2008133418A - Resin composition and flexible wiring board using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a halogen-free resin composition excellent in reliability under high temperature and humidity conditions and screen printability, and a flexible wiring board using a cured membrane of the resin composition as a protective membrane. <P>SOLUTION: The resin composition comprises component (A) of a resin containing a polycarbonate skeleton, component (B) of a metal hydroxide, component (C) of talc, and component (D) of a solvent, and the content of the component (B) is 20 or more and less than 100 wt.% based on the component (A) and the content of the component (C) is 20 to 100 wt.% based on the component (A). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition that does not use a halogen-based flame retardant and a flexible wiring board using a cured film of the resin composition as a protective film.

  In the field of electronic components, in response to miniaturization, thinning, and high speed, instead of epoxy resin as a resin for film forming resin composition with excellent heat resistance, electrical properties and moisture resistance, polyimide resin and polyamideimide resin Polyamide resin is 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.

  On the other hand, recently, printed wiring boards used for electric and electronic devices are required to have flame retardancy from the viewpoint of preventing fire and maintaining safety. In order to ensure the flame retardancy of the flexible wiring board, a halogen-based flame retardant is generally used (see, for example, Patent Document 4 and Patent Document 5).

  However, since halogen-based flame retardants may generate harmful gases during combustion, the use of materials that do not use them is desired.

JP 62-106960 A Japanese Patent Laid-Open No. 08-012763 JP 07-196798 A JP 2002-249639 A Japanese Patent Laid-Open No. 2003-213078

  The present invention has been made in view of the above-described conventional circumstances, and its problem is that it is excellent in non-halogen flame retardancy and printability under high-temperature and high-humidity conditions, and does not contain a halogen atom, and a flexible composition using the same. It is to provide a wiring board.

  In order to achieve the above object, the resin composition according to the present invention comprises (A) component: a resin containing a polycarbonate skeleton, (B) component: metal hydroxide, (C) component: talc, and (D ) Component: a solvent, the content of the component (B) is 20 to less than 100% by weight with respect to the component (A), and the content of the component (C) is 30 with respect to the component (A). It is characterized by being ~ 100% by weight.

  Further, in the resin composition having the above-described structure, in order to improve the bleeding that is one of the printability characteristics, the component (D) is preferably a monoterpene solvent, It is desirable that it is 5 to 20% by weight with respect to the solvent weight.

  In the resin composition having the above-described configuration, in order to improve the heat resistance, electrical properties, moisture resistance, and flexibility of the cured coating, the component (A) is represented by the following general formula (1).

（式中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基を示し、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樹脂を含有することが、望ましい。

(In the formula, a plurality of R's each independently represents an alkylene group having 1 to 18 carbon atoms, a plurality of X's each independently represents an alkylene group or arylene group having 1 to 18 carbon atoms, and m and n Each independently represents an integer of 1 to 20).

  Moreover, the flexible wiring board of this invention has the cured film which hardened | cured the said resin composition as a protective film, It is characterized by the above-mentioned.

  According to the present invention, it is possible to provide a resin composition excellent in non-halogen flame retardancy and printability under high temperature and high humidity conditions, and a flexible wiring board using the resin composition.

As described above, the resin composition according to the present invention includes (A) component: resin containing a polycarbonate skeleton, (B) component: metal hydroxide, (C) component: talc, and (D) component: The content of the component (B) is 20 to less than 100% by weight with respect to the component (A), and the content of the component (C) is 25 to 100% with respect to the component (A). %.
Hereinafter, each essential component of the resin composition will be described in detail.

((A) component: resin containing polycarbonate skeleton)
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. For example, urethane resin, polyimide resin, polyamideimide resin, polyamide resin, or 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 a derivative thereof” used as the component (a) is not particularly limited. For example, the following formulas (2) and (3):

（式（２）及び（３）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 (2) and (3), 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 (4):

（式（４）中、Ｙ²は、下記式（５）：

(In formula (4), Y ² represents the following formula (5):

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 (6):

（式（６）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 (6), 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 1-20.) 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 (6) is represented by the following formula (7):

（式（７）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（８）：
ＯＣＮ−Ｘ−ＮＣＯ （８）
（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 (7), R is an alkylene group having 1 to 18 carbon atoms, and m is an integer of 1 to 20), and the following formula (8):
OCN-X-NCO (8)
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 (8) 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 the carbonate diols represented by the above formula (7) 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 (8) 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 (8) 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 (8) 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 (7) and the diisocyanates represented by the above formula (8) 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 (7) and the diisocyanates represented by the formula (8) 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 (VII), 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 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 (1) is used as the component (a) and the compound (b-1) is used as the component (b), 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、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 (9), each R is 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 (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 (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) And Y ¹ is —CH ₂ —, —CO—, —SO ₂ —, or —O—).

  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、Ｙ²は、前記式（５）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 (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) Y ² is a group selected from a plurality of groups represented by the formula (5)), and a polyimide resin having a repeating unit represented by the formula (5) can be obtained.

  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 thereof 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. 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.

  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.

((B) component: metal oxide)
As the metal hydroxide which is the component (B) of the present invention, metal hydroxides such as magnesium hydroxide, aluminum hydroxide and hydrotalcite (manufactured by Sakai Chemical Co., Ltd., trade name “hydrotalcite”) are suitable. Used for. The metal hydroxide may be used alone, but in some cases, several kinds may be used together, and the addition amount is 20% by weight to less than 100% by weight with respect to the resin solid content of the component (A). 30 wt% to 90 wt% is preferable, and 40 to 80 wt% is more preferable. If it is less than 20% by weight, the flame-retardant effect is hardly exhibited, and if it exceeds 100% by weight, the printability and workability tend to decrease.

((C) component: talc)
The resin composition of this invention contains the talc which is (C) component as an inorganic filler from a viewpoint which can improve printability.
The content of talc as component (C) is 25% to 100% by weight with respect to the resin solid content as component (A), more preferably 30% to 80% by weight, and 40 to 70% by weight. Is particularly preferred. If the amount is less than 20% by weight, the printability tends to decrease, and if it exceeds 100% by weight, the workability tends to decrease.

  In the resin composition of this invention, in order to improve various characteristics, inorganic fillers other than the talc which is (C) component can also be used together, and you may use an organic filler together.

Examples of inorganic fillers other than talc as component (C) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), and 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), zirconate titanate lead lanthanum (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 zirco Near _{(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 can be used, and one or more of these can also be used.

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

  As a method of dispersing the above-mentioned inorganic filler and / or organic filler in the thermosetting resin solution, roll kneading, mixer mixing, etc., which are usually performed in the paint field, are applied and sufficient dispersion is performed. That's fine.

((D) component: solvent)
Examples of the solvent (D) used in the resin composition of the present invention include non-nitrogen-containing polar solvents, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol, diethyl ether, and triethylene glycol diethyl ether; dimethyl sulfoxide, diethyl Sulfur-containing solvents such as sulfoxide, dimethylsulfone and sulfolane; ester solvents such as γ-butyrolactone and 2- (2-n-butoxyethoxy) ethyl acetate and cellosolve; ketone solvents such as cyclohexanone and methyl ethyl ketone; toluene and xylene Aromatic hydrocarbon solvents such as monoterpene solvents such as limonene and the like, and these can be used alone or in combination of two or more.
Among the above solvents, from the viewpoint of printability, it is preferable to use a monoterpene solvent. When the monoterpene solvent is included, the content of the monoterpene solvent is preferably 5 to 20% by weight and more preferably 8 to 15% by weight with respect to the total solvent weight.

(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” and the like, 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 .; 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” 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 amount of these epoxy resins used is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, and even more preferably 3 to 100 parts by weight of the “resin containing an imide bond” used as the component (A). 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 tend to decrease, and when it exceeds 50 parts by weight, the heat resistance and viscosity stability tend to decrease. is there.

  As an addition method of the epoxy resin, the epoxy resin to be added may be added after being dissolved in the same organic solvent as the organic solvent that dissolves the “resin containing an imide bond” used as the component (A). It may be added directly.

Moreover, in the resin composition concerning this invention, in order to improve various characteristics, an antifoamer or a leveling agent other than the said component can be used.
As commercial products of such an antifoaming agent or leveling agent, “KS-602A”, “KS-603”, “KS-608”, “FA600” (above, trade names manufactured by Shin-Etsu Chemical Co., Ltd.), “ “BYK-A506”, “BYK-A525”, “BYK-A530”, “BYK-A500”, “BYK-A500”, “BYK-A501”, “BYK-A515”, “BYK-A555”, “Byketol-” “OK” (trade name, manufactured by Big Chemie Japan Co., Ltd.), “ARUFON UP-1000” (trade name, manufactured by Toa Gosei Co., Ltd.) and the like are preferably used. Absent.

The antifoaming agent or leveling agent may be used alone, but in some cases, several kinds may be used in combination, and the addition amount is preferably 1% by weight to 25% by weight based on the solid content of the resin composition, 5
More preferred is 18% by weight. When the addition amount is less than 5% by weight, the defoaming property and film forming property tend to be lowered. When the added amount exceeds 18% by weight, the defoaming property is improved, but the shape retaining property tends to be lowered.

Each of the resin compositions according to the present invention is suitably used as a protective resin composition for flexible wiring boards. In this resin composition, in order to improve the workability at the time of coating and the film properties before and after film formation, colorants such as epoxy resin, phenol resin, dye or pigment, heat stabilizer,
Antioxidants, flame retardants, lubricants and the like can also be added.

  Moreover, the flexible wiring board of the present invention is characterized in that the resin composition of the present invention is screen-printed on the wiring pattern of the flexible wiring board, and then thermally cured to form a cured film to form a protective film. . The conditions for thermosetting are preferably 80 to 160 ° C., more preferably 120 to 150 ° C. from the viewpoint of obtaining low warpage and flexibility suitable as a protective film. This range is not particularly limited, and can be cured in the range of 50 to 200 ° C., further 50 to 170 ° C., for example, if the above viewpoint is excluded.

  The heating time is preferably 60 to 150 minutes and more preferably 80 to 120 minutes from the viewpoint of obtaining low warpage and flexibility suitable as a protective film. This range is not particularly limited, and if the above viewpoint is excluded, curing can be performed in the range of 1 to 1000 minutes, preferably 5 to 300 minutes, and further 10 to 150 minutes.

  Each of the resin compositions of the present invention having the above-described configuration is, for example, an overcoat material for electronic parts, a liquid sealing material, an varnish for enamel wire, an impregnating varnish for electrical insulation, a casting varnish, mica, glass cloth, etc. It can be used for electronic parts such as sheet varnishes combined with base materials, varnishes for MCL laminates, friction material varnishes, interlayer insulating films, surface protective films, solder resist layers, etc. Used for.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the Example shown below is an illustration for demonstrating this invention suitably, Comprising: This invention is not limited at all.

(Example 1)
Into 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 were charged, and the temperature was raised to 140 ° C. Then, it was made to react at 140 degreeC for 5 hours, and diisocyanate was obtained. Furthermore, 288.20 g (1.50 mol) of trimellitic anhydride and 125.14 g (0.50 mol) of 4,4′-diphenylmethane diisocyanate and 1361.14 g of γ-butyrolactone were added to this reaction solution, and the temperature was raised to 160 ° C. After warming, it was reacted for 6 hours to obtain a resin having a number average molecular weight of 18,000. The obtained resin was diluted with 2- (2-n-butoxyethoxy) ethyl acetate to obtain a resin solution having a viscosity of 260 Pa · s and a nonvolatile content of 54% by weight.

  An amine type epoxy resin (product name “YH-434”, manufactured by Toto Kasei Co., Ltd., epoxy equivalent of about 120, 4 epoxy groups / molecule) is 10% by weight with respect to 100% by weight of the resin content of the obtained resin solution. 2- (2-n-Butoxyethoxy) ethyl acetate was added, a monoterpene solvent was added so as to be 12% by weight based on the total amount of solvent, and talc (Nippon Talc Co., Ltd.) was added to 100% by weight of the resin content. ), Average particle size 4.7 μm) 70% by weight and magnesium hydroxide (manufactured by Sakai Chemical Co., Ltd., average particle size 1.0 μm or less) 50% by weight were added, and 2- (2-n-butoxyethoxy) ethyl was added. The mixture was first kneaded roughly and then kneaded three times using a high-speed three-roll machine to perform main kneading to obtain a resin composition (R-1) in which talc and magnesium hydroxide were uniformly dispersed.

(Example 2)
In Example 1, except that 50% by weight of hydrotalcite was used as the metal hydroxide as component (B), the same material as in Example 1 was used, and the resin composition was subjected to the same steps as in Example 1. A product (R-2) was obtained.

(Example 3)
In Example 1, except that 20% by weight of magnesium hydroxide was used as the metal hydroxide as component (B), the same material as in Example 1 was used, and the resin composition was subjected to the same steps as in Example 1. A product (R-3) was obtained.

Example 4
In Example 2, except that 20% by weight of hydrotalcite was used as the metal hydroxide as the component (B), the same material as in Example 2 was used, and the resin composition was subjected to the same steps as in Example 2. A product (R-4) was obtained.

(Example 5)
In Example 1, except that 100% by weight of magnesium hydroxide was used as the metal hydroxide as component (B), the same material as in Example 1 was used, and the resin composition was subjected to the same steps as in Example 1. A product (R-5) was obtained.

(Example 6)
In Example 2, except that 100% by weight of hydrotalcite was used as the metal hydroxide as component (B), the same material as in Example 2 was used, and the resin composition was subjected to the same steps as in Example 2. A product (R-6) was obtained.

(Example 7)
In Example 1, the same material as in Example 1 was used except that 20% by weight of magnesium hydroxide was used as the metal hydroxide as component (B) and 20% by weight of talc as component (C) was used. And the resin composition (R-7) was obtained through the process similar to Example 1. FIG.

(Example 8)
In Example 2, the same material as in Example 2 was used, except that 20% by weight of hydrotalcite was used as the metal hydroxide as component (B) and 20% by weight of talc as component (C) was used. And the resin composition (R-8) was obtained through the process similar to Example 2. FIG.

Example 9
In Example 1, the same material as in Example 1 was used except that 50% by weight of magnesium hydroxide was used as the metal hydroxide as component (B) and 20% by weight of talc as component (C) was used. And the resin composition (R-9) was obtained through the process similar to Example 1. FIG.

(Example 10)
In Example 2, the same material as in Example 2 was used, except that 50% by weight of hydrotalcite was used as the metal hydroxide as component (B) and 20% by weight of talc as (C) was used. The resin composition (R-10) was obtained through the same steps as in Example 2.

(Example 11)
In Example 1, the same material as in Example 1 was used except that magnesium hydroxide was used at 100% by weight as the metal hydroxide as component (B) and 20% by weight of talc as component (C) was used. And the resin composition (R-11) was obtained through the process similar to Example 1. FIG.

(Example 12)
In Example 2, the same material as in Example 2 was used except that 100% by weight of hydrotalcite was used as the metal hydroxide as component (B) and 20% by weight of talc as component (C) was used. And the resin composition (R-12) was obtained through the process similar to Example 2. FIG.

(Example 13)
In Example 1, the same material as in Example 1 was used, except that 20% by weight of magnesium hydroxide was used as the metal hydroxide as component (B) and 100% by weight of talc as (C) was used. The resin composition (R-13) was obtained through the same steps as in Example 1.

(Example 14)
In Example 2, the same material as in Example 2 was used except that 20% by weight of hydrotalcite was used as the metal hydroxide as component (B) and 100% by weight of (C) talc was used. A resin composition (R-14) was obtained through the same steps as in Example 2.

(Example 15)
In Example 1, the same material as in Example 1 was used except that 50% by weight of magnesium hydroxide was used as the metal hydroxide as component (B) and 100% by weight of talc as component (C) was used. And the resin composition (R-15) was obtained through the process similar to Example 1. FIG.

(Example 16)
In Example 2, the same material as in Example 2 was used except that 50% by weight of hydrotalcite was used as the metal hydroxide as component (B) and 100% by weight of talc as component (C) was used. And the resin composition (R-16) was obtained through the process similar to Example 2. FIG.

(Example 17)
In Example 1, the same material as in Example 1 was used except that 100% by weight of magnesium hydroxide was used as the metal hydroxide as component (B) and 100% by weight of talc as (C) was used. The resin composition (R-17) was obtained through the same steps as in Example 1.

(Example 18)
In Example 2, the same material as in Example 2 was used, except that 100% by weight of hydrotalcite was used as the metal hydroxide as component (B) and 100% by weight of talc as (C) was used. The resin composition (R-18) was obtained through the same steps as in Example 2.

(Example 19)
Except that the monoterpene solvent used as the component (D) in Example 1 was added to 8% of the total amount of the solvent, the same material as in Example 1 was used, and the same process as in Example 1 was performed. After that, a resin composition (R-19) was obtained.

(Example 20)
Except that the monoterpene solvent used as the component (D) in Example 2 was added to 8% of the total amount of the solvent, the same material as in Example 2 was used, and the same process as in Example 2 was performed. A resin composition (R-20) was obtained.

(Example 21)
Except that the monoterpene solvent used as the component (D) in Example 1 was added to 20% of the total amount of the solvent, the same material as in Example 1 was used, and the same process as in Example 1 was performed. After that, a resin composition (R-21) was obtained.

(Example 22)
Except that the monoterpene solvent used as the component (D) in Example 2 was added to 20% of the total amount of the solvent, the same material as in Example 2 was used, and the same process as in Example 2 was performed. After that, a resin composition (R-22) was obtained.

(Example 23)
Except that the monoterpene solvent used as the component (D) in Example 1 was added to 0% of the total amount of the solvent, the same material as in Example 1 was used, and the same process as in Example 1 was performed. After that, a resin composition (R-23) was obtained.

(Example 24)
Except that the monoterpene solvent used as the component (D) in Example 1 was added to 25% of the total amount of the solvent, the same material as in Example 1 was used, and the same process as in Example 1 was performed. A resin composition (R-24) was thus obtained.

(Comparative Example 1)
In Example 1, except that 110% by weight of magnesium hydroxide was used as the metal hydroxide as component (B), the same material as in Example 1 was used, and the resin composition was subjected to the same steps as in Example 1. A product (R-25) was obtained.

(Comparative Example 2)
In Example 2, the same material as in Example 1 was used except that 110% by weight of hydrotalcite was used as the metal hydroxide as component (B), and the resin composition was subjected to the same steps as in Example 1. A product (R-26) was obtained.

(Comparative Example 3)
In Example 1, except that 10% by weight of magnesium hydroxide was used as the metal hydroxide as component (B), the same material as in Example 1 was used, and the resin composition was subjected to the same steps as in Example 1. A product (R-27) was obtained.

(Comparative Example 4)
In Example 2, the same material as in Example 1 was used except that 10% by weight of hydrotalcite was used as the metal hydroxide as component (B), and the resin composition was subjected to the same steps as in Example 1. A product (R-28) was obtained.

(Comparative Example 5)
A resin composition (R-29) was obtained through the same steps as in Example 1 except that 10% by weight of talc as component (C) was used in Example 1, and the same material as in Example 1 was used. Obtained.

(Comparative Example 6)
The resin composition (R-30) was obtained through the same steps as in Example 1 except that 110% by weight of talc as component (C) was used in Example 1, and the same material as in Example 1 was used. Obtained.

  The properties of the resin compositions (R-1) to (R-30) obtained in the above Examples and Comparative Examples were measured and evaluated by the following methods. The results are shown in (Table 1) to (Table 8).

(Defoaming property)
Tin-plated with comb-shaped wiring with 60 μm pitch (L / S = 30 μm / 30 μm) (
Flash plating) The resin composition obtained in each example was applied to a TAB base material with a printing press (trade name “LZ-045” manufactured by Neurong Co., Ltd.) and a mesh plate (manufactured by Murakami Co., Ltd., 150 mesh). A 25 mm square was printed at a printing speed of 100 mm / sec, dried for 3.5 minutes at 90 ° C. in an air atmosphere, and then heated and cured at 150 ° C. for 90 minutes in an air atmosphere to obtain a resin coating. The surface state of the obtained resin coating was observed using a universal projector (Nikon Corporation, magnification 50 times). The evaluation results are shown as ◯: no pinhole on the surface and x: pinhole on the surface.

(Exudation)
(1) A versatile projector near the edge of a cured film (sample) F obtained by printing and curing a resin composition on a wiring board (TAB substrate) B in the same manner as described above (defoaming property) (Nikon Corp., magnification 100 times), and as shown in FIG. 1, the size of the resin paste that exudes from the application region A due to capillary action with a capillary between adjacent wires w as a capillary L (μm) was measured and evaluated by its dimensions. It shows that it is so favorable that a dimension value is small.

(Reliability test)
Printing the resin composition obtained on a tin-plated (flash plating) TAB substrate having comb-shaped wiring with a pitch of 60 μm (L / S = 30 μm / 30 μm) so that the film thickness after curing is 20 μm, Curing was performed at 150 ° C. for 90 minutes. The obtained TAB base material on which the cured film was formed was placed in an environment of a temperature of 130 ° C. and a humidity of 85%, a voltage of DC 100 V was continuously applied, and the insulation resistance after 100 hours was evaluated. Three evaluations were made for the same resin composition, and the ratio of the number of those having an insulation resistance of 10 ⁷ Ω or more after 100 hours was defined as reliability. All 3 pieces are held at 10 ⁷ Ω or more: 100%, 2 pieces are held at 10 ⁷ Ω or more: 66%, one piece is held at 10 ⁷ Ω or more: 33%, all 3 pieces are below 10 ⁷ Ω: 0%

(Flame retardance)
A sample is printed on a two-layer TAB substrate [75 μm thick polyimide film, adhesive thickness 22 μm] obtained by etching a copper foil of a three-layer TAB substrate for a combustion test, and after curing at 150 ° C./90 min, a length of 127 mm, Five test pieces cut to a width of 12.7 mm were prepared. The combustion test was performed according to the UL94 vertical test standard.

  As shown in (Table 1) to (Table 8), the example is installed in an environment of a temperature of 130 ° C. and a humidity of 85%, and the insulation resistance is reduced even if the voltage of DC 100 V is continuously applied for 100 hours. It is clear to hold. It is also clear that the printability and flame retardancy are good. On the other hand, in a comparative example, a flame retardance falls and printability falls.

  As described above, the resin composition of the present invention is excellent in non-halogen flame retardancy, screen printability and reliability under high temperature and high humidity conditions. Therefore, the flexible wiring board formed with a cured film using the resin composition of the present invention has excellent reliability.

It is a figure which shows the evaluation method of the bleeding of the resin paste at the time of using the resin composition obtained by the Example and the comparative example for the cured film formation of a wiring board.

Explanation of symbols

A Application area B Wiring board (TAB base material)
F Cured film (sample)
w Wiring

Claims (6)

  Component (A): A resin containing a polycarbonate skeleton, Component (B): Metal hydroxide, Component (C): Talc, Component (D): A solvent, and the content of the component (B) is (A) 20 to less than 100 weight% with respect to a component, Content of the said (C) component is 20 to 100 weight% with respect to (A) component, The resin composition characterized by the above-mentioned.   The resin composition according to claim 1, wherein the component (D) contains a monoterpene solvent.   3. The resin composition according to claim 1, wherein the content of the monoterpene-based solvent is 5 to 20% by weight with respect to the total solvent weight. 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 any one of claims 1 to 3, wherein m and n each independently include a structural unit represented by an integer of 1 to 20.   It is a resin composition for flexible wiring board film formation, The resin composition of any one of Claims 1-4 characterized by the above-mentioned.   A flexible wiring board comprising the cured film of the resin composition according to claim 1 as a protective film.

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