WO2008047866A1

WO2008047866A1 - Resin composition and coating-film-forming material comprising the same

Info

Publication number: WO2008047866A1
Application number: PCT/JP2007/070346
Authority: WO
Inventors: Susumu Kaneko; Tomohiro Hirata; Munemaru Sakayori
Original assignee: Hitachi Chemical Company, Ltd.
Priority date: 2006-10-19
Filing date: 2007-10-18
Publication date: 2008-04-24
Also published as: KR20120021331A; KR20090053929A; JPWO2008047866A1; TW200835733A

Abstract

Disclosed is a resin composition showing excellent reliability even under high-temperature/constant-humidity conditions. Also disclosed is a material for forming a coating film, which comprises the resin composition. The resin composition comprises a resin, an inorganic microparticle and a triazinethiol derivative. The triazinethiol derivative is preferably a compound represented by the general formula (1). Wherein R1 represents -SH or -N(R2R3); and R2 and R3 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group which may have a substituent. The triazinethiol derivative is preferably used in an amount ranging from 0.1 to 5.0 wt% relative to the total solid content of the resin composition.

Description

Specification

Resin composition and film-forming material containing the same

Technical field

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.

Background art

[0002] In the field of electronic components, in response to miniaturization, thinning, and high speed, instead of epoxy resin as a resin with excellent heat resistance, electrical characteristics, and moisture resistance, polyimide resin, polyamideimide resin, polyamide resin Is used. These resins have a rigid resin structure. Therefore, when used to form a thin film on the surface of a substrate, the substrate after the thin film is greatly warped, and the formed cured film lacks flexibility and is not flexible. There is an inferior problem. Therefore, 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 polyamide-imide resin having a modified and flexible and low elastic modulus by modifying the resin has been proposed! / For example, it is disclosed in Patent Document 1, Patent Document 2, and Patent Document 3. Fillers are added to these resins to improve heat resistance and moisture resistance.

[0003] In recent years, electronic devices have become smaller, thinner, and faster, and FPC (Flexible Printed Circuit)

: Flexible circuit board), TAB (Tape

Automated Bonding: mounting technology for bonding semiconductor chips and circuit boards via tape-like film) and COF (Chip On Film: driver IC mounted on a film-like printed wiring board) . As can be seen from these technologies, the wiring pitch of flexible wiring boards has become even finer, and the thickness of the wiring has also become thinner.

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, if fine pitch wiring with a pitch of 40 am or less is used in order to realize the above-described high definition, even if an insulating protective film is formed using a conventional thermosetting resin paste, this insulating protective film If voltage is applied to the wiring under high-temperature and high-humidity conditions where the high-temperature and humidity resistance is not sufficient, There was a problem that insulation between the wires deteriorated and insulation reliability could not be maintained for a long time!

Patent Document 1: Japanese Patent Application Laid-Open No. 62-106960

Patent Document 2: Japanese Patent Application Laid-Open No. 08-012763

Patent Document 3: Japanese Patent Laid-Open No. 07-196798

Disclosure of the invention

Problems to be solved by the invention

[0006] The present invention has been made in view of the above-described conventional problems, and its object 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. There is.

Means for solving the problem

[0007] In order to solve the above-mentioned problems, the resin composition according to the present invention is characterized by comprising a resin (A), inorganic fine particles (B), and a triazine thiol derivative (C). .

[0008] The triazine thiol derivative (C) is preferably a compound represented by the following general formula (1).

[0009] [Chemical 1]

(Wherein 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 good aryl group is shown.)

[0010] The content of the triazine thiol derivative (C) is preferably 0.1 wt% to 5 wt% with respect to the total solid content of the resin composition.

[0011] In the resin composition of the present invention, the resin (A) preferably contains a polycarbonate skeleton.

[0012] Further, in the resin composition of the present invention, the resin (A) is a polyurethane represented by the following general formula (2): It preferably includes a structure.

[Chemical 2]

0 0 0

r II II II ζ,

—X— NC-O + R—O— C-O ^ R— OCN + (2)

HH ^Π

(Wherein 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) is there. )

[0013] The resin (A) is selected from the group consisting of polyimide resin, polyamideimide resin, polyamide resin, modified polyimide resin, modified polyamideimide resin, and modified polyamide resin. Is preferred.

[0014] The resin composition of the present invention preferably further contains a solvent (D).

[0015] The resin composition of the present invention preferably further contains an epoxy resin (E).

[0016] The resin composition of the present invention is preferably a resin composition for forming a film on a flexible wiring board.

[0017] Further, the film-forming material of the present invention is characterized by containing the resin composition of the present invention.

The invention's effect

[0018] The resin composition and the film-forming material of the present invention are excellent in printability, workability, and insulation reliability, and can form a film having high temperature and humidity resistance and good surface wettability. Overcoat material for electronic parts, liquid encapsulant, varnish for enameled wire, impregnated varnish for electrical insulation, varnish for laminated plate, varnish for friction material, interlayer insulation film in printed circuit board field, surface It can be suitably used for forming various films on electronic parts such as protective films, solder resist films, adhesive layers, and semiconductor elements. It is particularly useful as a protective film for flexible wiring boards for COF applications.

BEST MODE FOR CARRYING OUT THE INVENTION

[0019] (Resin (A))

Heat resistance, electrical properties, moisture resistance, solvent resistance of the cured film formed from the resin composition and In order to improve chemical resistance, the ability to introduce a component capable of improving heat resistance into the main chain of the resin S is mentioned, and examples of the resin (A) include urethane resin, polyimide resin, polyamideimide resin or Polyamide resins or resins having these skeletons are preferred. Among them, a resin having a polycarbonate skeleton and a urethane bond is preferable from the viewpoint of flexibility and low elastic modulus. Further, from the viewpoint of increasing heat resistance, a resin containing an imide bond is more preferable.

[0020] In the present invention, the "resin containing a polycarbonate skeleton" that can be used as the component (A) is usually a compound having a carboxyl group at the terminal, such as 1,6-hexanediol-based polycarbonate diol, It can be obtained by reacting with a compound having an acid anhydride 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 one or more compounds selected from tetravalent polycarboxylic acids having an acid anhydride group and (b) component: an isocyanate compound or an amine compound.

[0022] The "trivalent polycarboxylic acid having an acid anhydride group and its derivative" used as the component (a) is not particularly limited. For example, the following formulas (3) and (4):

[0023] [Chemical 3]

(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 1 O)

The compound shown by these can be used.

[0025] "Trivalent polycarboxylic acid having an acid anhydride group" used as component (a) above

Trimellitic anhydride is particularly preferable from the viewpoints of heat resistance and cost.

[0026] The "tetravalent polycarboxylic acid having an acid anhydride group" used as the component (a) is not particularly limited. For example, the following formula (5):

[0027] [Chemical 5

0 0

0 (5)

,

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

[0028] [Chemical 6]

It is possible to use a tetracarboxylic dianhydride represented by the following formula: These can be used alone or in combination of two or more. [0029] In addition to these, as necessary, as an acid component, aliphatic dicarboxylic acid (succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decanedioic acid, dodecanedioic acid, Dimer acid, etc.) and 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.

[0030] The isocyanate compound used as the component (b) is, for example, the following formula (7): [0031] [Chemical Formula 7]

0 0 0

OCN- X-N

H

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

[0032] The "compound having a polycarbonate skeleton and a urethane bond" represented by the above formula (7) is represented by the following formula (8):

[0033] [Chemical 8]

HO + R-0-

(In the 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)

(Wherein X is a divalent organic group) is obtained by reacting with diisocyanates.

[0034] Examples of the divalent organic group represented by X in the above formula (9) include, for example, an alkylene group having 1 to 20 carbon atoms, or a lower alkyl having 1 to 5 carbon atoms such as an unsubstituted or methyl group. And arylene groups such as a phenylene group substituted with a group. The number of carbon atoms of the alkylene group is more preferably 1 to 18; Diphenylmethane 1,4'-diyl group, hydrogenated diphenylmethane —4,4 ′ diyl group, diphenylsulfone— Groups having two aromatic rings such as 4,4 ′ diyl group are also preferred.

Examples of the carbonate diols represented by the above formula (8) include α, ω poly (hexamethylene carbonate) diol, α, ω-poly (3-methyl-pentamethylene force-bonate) diol, and the like. Examples of the commercially available products include “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.

[0036] The diisocyanates represented by the above formula (9) include, for example, diphenylmethane-2, 4, 1, diisocyanate; 3, 2, 1, 3, 3, 1, 4, 2, 1, 4, 3 , 1, 5, 2, 1, 5, 3, 1, 6, 2'- or 6, 3'-dimethyldiphenylmethane 2, 4'-diisocyanate; 3, 2 '1, 3, 3, 1, 4 , 2, 1, 4, 3, 1, 5, 2, 1, 5, 3, 1, 6, 2, 1 or 6, 3, 1 ethynole diphenylmethane 1, 2, 4, 1 diisocyanate; 3, 2, 1, 3, 3, 1, 4, 2, 1, 4, 3, 1, 5, 2 '—, 5, 3' —, 6, 2 'or 6, 3'-dimethoxydiphenylmethane 2, 4'— Diphenylmethane; 4,4'-diisocyanate; diphenylmethane, 1,3,1, diisocyanate; diphenylmethane diisocyanate compounds such as diphenylmethane 3,4'-diisocyanate and the like Diphenyl ether 4, 4'-diisocyanate; benzophenone 4, 4'-diisocyanate; diphenyl sulfone 1,4'-diisocyanate; tolylene 2,4 diisocyanate; tolylene 2,6 diisocyanate; m 4, 4′-one [2, 2 bis (4 phenoxyphenol) 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.

[0037] In addition, the diisocyanates represented by the above formula (9) are within the scope of the object of the present invention. Aliphatic or alicyclic isocyanates such as lysine diisocyanate, or trifunctional or higher polyisocyanate can be used.

[0038] The diisocyanates represented by the above formula (9) may be those stabilized with a blocking agent necessary to avoid changes over time. As a blocking agent, there are no particular limitations on the power of alcohol, phenol, oxime, and the like.

[0039] The blending ratio of the carbonate diol represented by the above formula (8) and the diisocyanate represented by the above formula (9) is the ratio of the number of hydroxyl groups to the number of isocyanate groups. Isocyanate groups / hydroxyl groups = 1.01 or more It is preferable that

[0040] The reaction between the carbonate diol represented by the above formula (8) and the diisocyanate 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 and the reaction conditions employed. For example, it can be 2-5 hours on a flask scale of! ~ 5 L (liter).

[0041] The number average molecular weight of the compound (b-1) (isocyanate compound) thus obtained is preferably 500-10,000, more preferably 1,000 to 9,500, Particularly preferred is 1,500-9,000. If the number average molecular weight is less than 500, the warping property tends to deteriorate, and if it exceeds 10,000, the reactivity of the isocyanate compound tends to decrease, and it tends to be difficult to make a polyimide resin.

In this specification, the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. The number average molecular weight and the degree of dispersion of the present invention are defined as follows.

a) Number average molecular weight (M)

n

M = ∑ (N M) / N = Σ ΧΜ.

(X = molar fraction of molecule of molecular weight M = N / ∑ N)

b) Weight average molecular weight

M = ∑ (NM ² ) / ∑NM = ∑WM.

(W = weight fraction of molecules with molecular weight M = N M / ∑ N M)

c) Molecular weight distribution (dispersity) Dispersity = M / M

w n

[0043] As the isocyanate compound of the component (b), a compound other than the compound (b-1) (hereinafter referred to as the 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). For example, diisocyanates represented by the formula (9), trivalent or higher polyisocyanates Etc. These can be used alone or in combination of two or more. The preferred range of the number average molecular weight of the isocyanate compound of the compound (b-2) is the same as that of the compound (b-1).

In particular, from the viewpoint of heat resistance, it is preferable to use the compound (b-1) and the compound (b-2) in combination. When compound (b-1) and compound (b-2) are used singly, compound (b-l) is used from the viewpoint of improvement of flexibility and warpage as a protective film for flexible wiring boards. ) Is preferably used.

[0045] As the compound (b-2), 50 to 100% by weight of the total amount thereof is an aromatic polyisocyanate. S is preferable. Balance between heat resistance, solubility, mechanical properties, cost, etc. In consideration, 4, A′-diphenylmethane diisocyanate is particularly preferred.

[0046] When the compound (b-1) and the compound (b-2) are used in combination, the equivalent weight of the compound (b-1) / compound (b-2) is 0. I / O. 9-0. 9 / 0.1 is preferable, and 0.2 / 0.8—0.8.8 / 0.2 is more preferable, and 0.3 / 0.7 to 0.7 / 0.3 is preferable. Particularly preferred. Equivalent specific force S If it is in this range, it can be obtained by force S to obtain film properties such as good low warpage and adhesion and good heat resistance.

[0047] Among the above component (b), the amine compound includes a compound obtained by converting an isocyanato group into an amino group in the isocyanate compound of the above component (b). Conversion of the isocyanato group to an amino group can be performed by a known method. The preferred number / average molecular weight of the amine compound is the same as that of the above compound (b-1).

[0048] The blending ratio of the component (a) "trivalent polycarboxylic acid having an acid anhydride group or derivative thereof and / or tetravalent polycarboxylic acid having an acid anhydride group" is (b The repulsive force of the total number of carboxyl groups and acid anhydride groups in component (a) relative to the total number of isocyanate groups in component) is preferably 0.6 to 1.4, and 0.7 to 1. To be 3 It is particularly preferable that the ratio is 0.8 to 1.2. If 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 the polyimide bond.

[0049] 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):

[0050] [Chemical 9]

(In the formula (10), 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 1 to 20) It is an integer.) A polyamideimide resin having a repeating unit represented by

[0051] 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):

[0052] [Chemical 10]

(In the 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 1 to 20) It is an integer, and Y ¹ is CH 1, CO—, —SO 1, or 1 O 2).

[0053] 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):

[0054] [Chemical 11] 2)

(In the 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 1 to 20) It is an integer, and Y ² is a polyimide resin having a repeating unit represented by a group selected from a plurality of groups represented by the above formula)).

[0055] Thus, the resin (Α) as the component (を) preferably includes a polyurethane structure represented by the following general formula (2) from the viewpoint of flexibility and low elastic modulus. Better!/,.

[Chemical 2]

0 0 0

r II II II,

-X-NC-0 R-0-C-0, R-0CN- _n (2)

H H

[0056] In the present invention, (a) component in the method for producing "resin containing an imide bond" used as component (A): a trivalent polycarboxylic acid having an acid anhydride group and The reaction between the derivative and one or more compounds selected from tetravalent polycarboxylic acids having an acid anhydride group and the component (b): an isocyanate compound or an amine compound is an organic solvent, preferably a nitrogen-free In the presence of a polar solvent, the carbon dioxide gas that is liberated and generated is removed from the reaction system and subjected to calothermal condensation.

[0057] Examples of the non-nitrogen-containing polar solvent include ethereal solvents such as diethylene glycol dimethyl ether, dimethylene glycoleno retino enoate, triethylene glucono resin methino ree enore, triethylene glucono lesino eno enoate; Sulfur-containing solvents such as dimethylenolesnoreoxide, dimethyl sulfoxide, dimethyl sulfone, and sulfolane; _エステル ester solvents such as butyrolatatane and cellosolve acetate; cyclohexanone, methyl ethyl keto Ketone solvents such as toluene; aromatic hydrocarbon solvents such as toluene and xylene, and the like. These can be used alone or in combination of two or more.

[0058] 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. In order to provide high volatility, impart low-temperature curability, and efficiently carry out the reaction in a homogeneous system, γ-petit-mouth rataton is most preferable.

[0059] The amount of the solvent used is preferably 0.8 to 5.0 times (weight ratio) of the resin to be produced. If it is less than 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, and if it exceeds 5.0 times, the reaction rate tends to decrease.

[0060] The reaction temperature is preferably from 80 to 210 ° C, preferably from 100 to 190 ° C, more preferably from 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.

[0061] 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.

[0062] Further, after the synthesis is completed, the isocyanate group at the resin end can be blocked with a blocking agent such as alcohols, ratatams, oximes, carboxylic acids, and acid anhydrides. As the component (A), it is preferable to use a thermosetting resin.

[0063] The number average molecular weight of the resin thus obtained is 15,000-50,000, preferably S, more preferably 20,000-45,000, more preferably 25,000-40 , 000 is particularly preferred, and 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 tinning tend to deteriorate, and if the number average molecular weight exceeds 50,000, it will be dissolved in a non-nitrogen-containing polar solvent. Easily insolubilized inside. In addition, workability tends to be inferior.

[0064] 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 the number average molecular weight of 15,000. It is preferably 0 or more. If 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.

[0065] The mixing ratio when mixing two or more resins having different number average molecular weights used in the present invention is not particularly limited 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.

[0066] 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 the inorganic fine particles (B) of the present invention. Preferably, it is 60 to 98 parts by weight, more preferably 70 to 95 parts by weight. If the content of the resin (A) is less than 50 parts by weight, the heat resistance and reliability tend to decrease, and if it exceeds 99 parts by weight, the curability tends to decrease.

[0067] (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 (

2 2 3 2

Ta 2 O), Zircoyu (ZrO 2), Silicon Nitride (Si N), Barium Titanate (BaO 1 TiO 2), Charcoal

2 5 2 3 4 2 Barium oxide (BaCO), lead titanate (PbO'TiO), lead zirconate titanate (PZT), titanium

3 2

Lead lanthanum zirconate (PLZT), gallium oxide (Ga 2 O 3), spinel (MgO 2 .Al 2 O 3)

2 3 2 3

, Mullite (3A1 O-2SiO), cordierite (2MgO '2Al O / 5SiO), talc (3

2 3 2 2 3 2

MgO -4SiO · 0), aluminum titanate (TiO— Al 2 O 3), yttria-containing zirconium

2 2 2 2 3

(Y O -ZrO), barium silicate (BaO '8SiO), boron nitride (BN), calcium carbonate

2 3 2 2

(CaCO), calcium sulfate (CaSO), zinc oxide (ZnO), magnesium titanate (Mg

3 4

O -TiO), barium sulfate (BaS0), organic bentonite, carbon (C), hydride mouth tulsa

twenty four

Can be used, and one or more of these can be used. Among these, barium sulfate is preferable from the viewpoint of improving the insulation reliability of the hardened film, which is preferable from the viewpoint of suppressing the flow of the paste after printing. [0068] As the inorganic particles (B) to be blended in the resin composition of the present invention, those having an average particle size of 50 am or less and a maximum particle size of 100 m or less are preferably used. When the average particle size exceeds 5 C ^ m, 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 size exceeds 100, the appearance and adhesion of the coating film of the resin composition are poor. There is a tendency to become insufficient. The average particle size is more preferably 30 111 or less, further preferably 1 O ^ m or less, particularly preferably or less, and the maximum particle size is more preferably 80 in or less, still more preferably 60 in or less, particularly preferably. Is less than 40 in.

[0069] The content of the inorganic particles used as the component (B) is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the component (A), preferably 20 to 180 parts by weight. 30 to 150 parts by weight is particularly preferable. 50 to 120 parts by weight is particularly 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 flow of paste after printing will increase, and the film thickness will tend to be thin. There is a tendency that the state and electrical characteristics of the film edge after the sparrow are inferior. Also, if the content of component (B) exceeds 200 parts by weight, the viscosity and thixotropy coefficient of the paste increase, the transferability of the paste to the substrate decreases, and voids and pinholes in the printed film increase. Tend to.

[0070] As a method of dispersing the inorganic particles (B) in the resin solution, roll kneading, mixer mixing, and the like, which are usually performed in the paint field, are applied, and sufficient dispersion is performed. In particular, the dispersion method is not limited.

[0071] (Triazinethiol derivative (C))

The triazine thiol derivative (C) blended in the resin composition of the present invention is not particularly limited, but a compound represented by the following general formula (1) is preferably used.

[0072] [Chemical 12]

(Wherein R ¹ represents SH and —N (R ² R ³ ). R ² and R ³ may each independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituent. [0073] Examples of the compound represented by the general formula (1) include 2, 4, 6 trimercapto s triazine, 2 dibutylamino 1, 4, 6 dimercapto s triazine, and 2 anilino. 1, 4, 6-dimercapto s-triazine and the like. Commercially available products of these compounds include “DISNET F” (trade name: 2, 4, 6 trimercapto-s-triazine) manufactured by Sankyo Kasei Co., Ltd., and “DISNET DB” (trade name: 2 dibutylamino-1). , 6 Dimercapto-s Triazine) and “Disnet AF” (trade name: 2 Anilino 4, 6 Dimercapto-s Triazine).

[0074] The triazine thiol derivative may be used alone, but depending on the case, the content that may be used in combination with several kinds of the resin composition is (B) the resin solid content excluding inorganic fine particles. The force S is preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight. 0. Less than 1% by weight makes it difficult to achieve the effect. If more than 5% by weight, the printability and workability deteriorate.

[0075] ((D) component: solvent)

In the resin composition of the present invention, various solvents can be used as the component (D). Solvents include non-nitrogen-containing polar solvents such as diethylene glycol dimethyl ether, diethylene glycolenole, jetinoreethenole, triethyleneglycolenolegetinoleatenole, etc .; dimethyl sulfoxide, jetyl sulfoxide, dimethyl sulfone, Sulfur-containing solvents such as sulfolane; ester solvents such as γ-petit-latatotone, acetic acid 2- (2-ηbutoxyethoxy) ethyl, and cellosolve acetate; ketone solvents such as cyclohexanone and methyl ethyl ketone; toluene, xylene, etc. Aromatic hydrocarbon solvents, such as monoterpene solvents such as limonene, and the like. These may be used alone or in combination of two or more.

Among the above solvents, from the viewpoint of printability, it is preferable to use γ-petit-mouth rataton.

[0076] (Other resin components)

In the resin composition of the present invention, various epoxy resins can be optionally added as the component (ii) in order to improve thermosetting. As an epoxy resin as a curing agent For example, bisphenol A type epoxy resin (trade name “Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.), bisphenol F type epoxy resin (trade name “YDF-170” manufactured by Tohto Kasei Co., Ltd.) ), Phenol nopolac type epoxy resin (trade name “Epicoat 152, 154” manufactured by Yuka Shell Epoxy Co., Ltd.); product name “EPPN-201” manufactured by Nippon Kayaku Co., Ltd .; manufactured by Dow Chemical Company Product name “DEN-438”, etc.) o Cresol nopolac type epoxy resin (product name “EOCN—125S, 103S, 104S”, etc., manufactured by Nippon Kayaku Co., Ltd.), polyfunctional epoxy resin (oil-based shell epoxy ( Product name “Eponl031S” manufactured by Chino Co., Ltd .; Product name “Araldite 0163” manufactured by Chino 'Specialty' Chemicals Co., Ltd .; Product names “Denacol EX—611, EX-614, EX-614B” manufactured by Nagase Chemical Co., Ltd. , EX—622, EX—512, EX—521, EX—421, EX-411, EX—321 ”, etc.), Type epoxy resin (product name “Epicoat 604” manufactured by Yuka Shell Epoxy Co., Ltd.); product name “YH434” manufactured by Tohto Kasei Co., Ltd .; product name “TETRAD—X” manufactured by Mitsubishi Gas Chemical Co., Ltd. “TERRAD—C”; trade name “GAN” manufactured by Nippon Kayaku Co., Ltd .; trade name “ELM—120” manufactured by Sumitomo Chemical Co., Ltd.), heterocyclic-containing epoxy resin “specialty” chemicals Trade name “ALALDITE PT810” manufactured by Co., Ltd.), cycloaliphatic epoxy tree moonlight (“ERL4234, 4299, 4221, 4206” manufactured by UCC, etc.) etc. Can be used in combination of more than one type. Among these epoxy resins, amine type epoxy resins having 3 or more epoxy groups in one molecule are particularly preferred in terms of improving solvent resistance, chemical resistance and moisture resistance!

[0077] 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 daricidyl ether, phenyl daricidyl ether, dibromo phenacidyl ether, dib-mouthed mocredyl glycidyl ether, and the like. In addition, alicyclic epoxy compounds such as 3,4 epoxycyclohexenole and methinole (3,4-epoxycyclohexane) force carboxylate can be used.

[0078] The content of these epoxy resins is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, still more preferably 3 to 40 parts by weight based on 100 parts by weight of the "resin" used as the component (A). It is assumed to be a heavy part. If the content of the epoxy resin is less than 1 part by weight, the curability, solvent resistance, Chemical properties and moisture resistance tend to decrease. When the amount exceeds 50 parts by weight, heat resistance and viscosity stability tend to decrease.

[0079] As an addition method of the epoxy resin, the epoxy resin to be added is used as the component (A) V, and it may be added after being dissolved in the same organic solvent as that for dissolving the "resin". It may also be added directly.

[0080] (Other additives)

The antifoaming agent or leveling agent added to the resin composition of the present invention includes “KS-602A”, “KS-603”, “KS-608”, “FA600” (above, manufactured by Shin-Etsu Chemical Co., Ltd.) : Product name), “: BYK—A506”, “: BYK—A525”, “: BYK—A530”, “: BYK—A500”, “: BY K—A500”, “: BYK—A501”, “: “BYK—A515”, “: BYK—A555”, “: Byketol—OK” (above, BYK-Chemichi 'Japan Co., Ltd .: trade name), “ARUFON UP-1000” (Toagosei Co., Ltd .: trade name), etc. Is preferably used, but is not particularly limited. The above antifoaming agent, leveling agent, etc. may be used alone, but in some cases, several types may be used in combination, preferably 0.05% by weight based on the solid content of the resin composition From 1 to 5% by weight, more preferably from 0.05 to 0.5% by weight is added. 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 retention is lowered.

[0081] 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 properties before and after the film formation, this resin composition has a colorant such as epoxy resin, phenol resin, dye or pigment, heat stabilizer, antioxidant. Agents, flame retardants, lubricants, etc. can also be added.

[0082] (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 overcoat materials for electronic parts, liquid encapsulants, varnishes for enamel wires, impregnating varnishes for electrical insulation, casting varnishes, dynamism, glass cloth, and sheet 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, etc. in the printed circuit board field. In addition, the resin composition for film formation or the film formation material is It can also be used for electronic components such as semiconductor elements, and is particularly useful as a protective film for flexible wiring boards for COF applications where the wiring pattern is tin-plated before forming the resin composition.

[0083] When the resin composition according to the present invention is used for a protective film of a flexible wiring board for COF in which the wiring pattern portion is tin-plated, the heating temperature condition of thermosetting prevents the diffusion of the tin plating layer, From the viewpoint of obtaining warpage and flexibility suitable as a protective film, 80 to 130 ° C. is preferred 90 to 120 ° C. is particularly preferred. In addition, the heating time for thermosetting is preferably 60 to 150 minutes from the viewpoint of preventing diffusion of the tin plating layer and obtaining warp and flexibility suitable as strength, protective film, and 80 to 150 minutes. Particularly preferred is 120 minutes

Yes

[0084] The film-forming material of the present invention is the resin composition of the present invention itself! /, Or other components may be added to the resin composition of the present invention as necessary.

[0085] 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 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 35 ° or less. Power to do S is preferable. When the contact angle with the liquid encapsulant is greater than 35 °, the liquid encapsulant becomes insufficiently wet and spread, for example, when used for semiconductor coating, it may sufficiently cover the periphery of the IC connection. become unable. The contact angle with the sealing material can be measured with a contact angle measuring device (manufactured by Kyowa Interface Science).

Example

Hereinafter, the present invention will be described in detail with reference to examples. The following examples are merely illustrative examples for favorably explaining the present invention, and do not limit the present invention.

[0087] (Example 1)

In a 5 liter four-necked flask equipped with a stirrer, a condenser with an oil / water separator, a nitrogen inlet tube 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 monole), 4, 4'-diphenol nitromethane diisocyanate 250 · 27 g (l.00 monole), γ-p, tirolatatone 833 · 51 g The temperature was raised to 140 ° C. The reaction was carried out at 140 ° C for 5 hours to obtain diisocyanate. [0088] Subsequently, trimellitic anhydride 288 · 20g (l.50 monole) and 4,4'-diphenylmethane diisocyanate 125 · 14g (0.50 monole) were added to the reaction solution (diisocyanate). Γ-butyrolatatane 1361.14 g was charged, and the temperature was raised to 160 ° C., followed by reaction for 6 hours to obtain a resin (resin (A)) having a number average molecular weight of 18,000. The obtained resin was diluted with a γ-bubble outlet to obtain a resin solution having a viscosity of 160 Pa's and a nonvolatile content of 52% by weight.

[0089] With respect to 100 parts by weight of the resin content of the obtained resin solution, an amine-type epoxy resin (Toto Kasei)

Product name “YH-434”, epoxy equivalent of about 120, 4 epoxy groups / molecule), 10 parts by weight and γ-petit-mouth rataton added, viscosity 100 Pa's, nonvolatile content 52% by weight A resin solution was obtained. Silica particles (made by Nippon Aerosil Co., Ltd., trade name “Aerosil 380”, average particle size of 0 · 2 111 or less) as inorganic particles (B) were added to 2373 g (resin solid content 1234 g) of the obtained resin solution 61. 7g, and barium sulfate particles (manufactured by Sakai Chemical Industry Co., Ltd., trade name “B-30, average particle size 0 · 3 ^ 111]) 185.3 g were added, first coarsely kneaded, then using a high-speed three roll Then, kneading was repeated three times and main kneading was performed to obtain a resin composition in which silica fine particles were uniformly dispersed.

[0090] After adding 234 g of "Disnet D Bj (trade name, manufactured by Sankyo Kasei Co., Ltd.)" as a triazine thiol derivative (C) to the resin composition obtained above, the mixture was rotated for 3 minutes with a revolving stirrer. The resin composition of the present invention was obtained by stirring.

[0091] (Example 2)

The resin of the present invention was treated in exactly the same manner as in Example 1 except that the content of “Disnet DB” (triazinethiol derivative (C)) in Example 1 was changed to 12.34 g. A composition was obtained.

[0092] (Example 3)

The resin of the present invention was prepared in exactly the same manner as in Example 1 except that the content of “Disnet DB” (triazinethiol derivative (C)) was 61.7 g in Example 1. Got the composition

Yes

[0093] (Example 4)

The same procedure as in Example 1 was performed except that 1.234 g of “disnet F” (trade name, manufactured by Sankyo Kasei Co., Ltd.) was added as a triazine thiol derivative (C) instead of “disnet DB”. The resin composition of the present invention was obtained. [Example 5]

A resin composition was obtained in 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]

A resin composition was obtained in the same manner as in Example 1, except that the content of “Gisnet F” in Example 4 was changed to 61.7 g.

[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]

The same operation as in Example 1 was carried out except that 12.34 g of dysnet F was added in Example 4 and 19.7 g of dysnet DB was added to obtain a resin composition.

[0098] (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!

[0099] The properties of the resin compositions 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).

[0100] (1) Printability

35 Each of the obtained resin compositions on a copper foil of 111, using a printing machine (trade name “LZ-045” manufactured by Neurong Co., Ltd.) and a mesh plate (150 mesh manufactured by Murakami Co., Ltd.) Printed at 10 mm square at a printing speed of 100 mm / sec, dried in air at 90 ° C for 30 minutes, and then cured by heating in air at 120 ° C for 60 minutes to form a resin film. For the resin film, the surface state was observed with a universal projector (Nikon Corporation magnification: 50 times). If there was no irregularity on the surface, it was rated as ◯, and if there was irregularity on the surface, it was evaluated as X. did.

[0101] (2) Insulation reliability test

L / S = 15 / m / 15 μm in copper wiring pattern! /, And the thickness of the cured resin composition is 10 to be m It was printed and heat cured 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. What was insulation resistance 10 ⁷ Omega more after 100 hours 〇, what was less than 1 0 ⁷ Omega was X.

[0102] (3) Wettability with sealing material (Contact angle)

Each obtained resin composition was applied onto a rough surface of electrolytic copper foil having a thickness of 35 Hm or a polyimide film having a thickness of 50 Hm and dried at 90 ° C for 15 minutes. Heated at ° C for 60 minutes, and cured epoxy coating (made by Hitachi Chemical Co., Ltd., trade name “CEL-C”) on the cured film (thickness 20-30 am) of each resin composition obtained. -5020 ”) was added dropwise, and 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 sealing material and cured film

X: There is a boundary between the sealing material and the cured film

[0103] [Table 1]

(table 1)

(Table 2)

[0105] From the above results, the following can be understood.

Examples;! 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 60 VDC was continuously applied for 100 hours. Therefore, it can be seen that the resin composition of the present invention and the resin film thereof show 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. It was. In addition, 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.

Industrial applicability

[0106] The resin composition for screen printing and the film-forming material of the present invention have the above-mentioned excellent properties, and include an overcoat material for electronic parts, a liquid encapsulant, an varnish for varnish electrical insulation for enameled wire, and a laminate. It is suitably used for electronic components such as varnish for plates, varnish for friction materials, interlayer insulating films, surface protective films, solder resist films, adhesive layers, etc. in the field of printed circuit boards, and semiconductor devices.

Claims

The scope of the claims

[1] A resin composition comprising a resin (A), inorganic fine particles (B), and a triazine thiol derivative (C).

[2] In the resin composition according to claim 1, the triazine thiol derivative (C) is represented by the following general formula (1):

[Chemical 1]

(Wherein 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 the formula:

[3] The resin composition according to claim 1, wherein the content of the triazine thiol derivative (C) is from 0.1% by weight to 5% by weight with respect to the total solid content of the resin component. Resin composition.

[4] The resin composition according to claim 1, wherein the resin (A) includes a polycarbonate skeleton.

[5] The resin composition according to claim 1, wherein the resin (A) includes a polyurethane structure represented by the following general formula (2).

2. The resin composition according to claim 1, wherein the resin (A) is a polyimide resin, a polyamide. A resin composition, wherein the resin composition is selected from the group consisting of doimide resin, polyamide resin, modified polyimide resin, modified polyamideimide resin, and modified polyamide resin.

[7] The resin composition according to claim 1, further comprising a solvent (D).

[8] The resin composition according to claim 1, further comprising an epoxy resin (E).

[9] A resin composition, wherein the resin composition according to claim 1 is a resin composition for forming a film on a flexible wiring board.

[10] A film-forming material comprising the resin composition according to claim 1.