KR101140738B1 - Polyester resin for semiconductor package substrate and film manufactured from the same - Google Patents

Abstract

The present invention provides a polyester resin comprising a structural unit of a fluorene group skeleton and a film for a semiconductor package substrate prepared therefrom. Since the film for semiconductor package substrates according to the present invention has low anisotropy, excellent heat resistance and improved solubility in organic solvents, it can be usefully used as a material of a multilayer circuit board for highly integrated semiconductor packages.

Description

Polyester resin for semiconductor package substrate and film made therefrom {POLYESTER RESIN FOR SEMICONDUCTOR PACKAGE SUBSTRATE AND FILM MANUFACTURED FROM THE SAME}

The present invention relates to a polyester resin for a semiconductor package substrate which is a printed circuit board (PCB) component among electrical and electronic components, and a film prepared therefrom. More specifically, the present invention relates to a resin for a semiconductor package substrate and a film prepared therefrom which can produce a liquid crystalline polyester film having high solubility in organic solvents and exhibiting excellent heat resistance.

Since liquid crystalline polyester resins exhibit excellent heat resistance, tensile strength, high frequency characteristics, low hygroscopicity, and the like, they have been widely used in electrical and electronic materials recently, and are particularly attracting attention as semiconductor package substrate materials. However, the conventional liquid crystalline polyester film produced by extrusion molding the liquid crystalline polyester is oriented remarkably in the longitudinal direction (pushing direction), so that the transverse direction (orthogonal to the pushing direction) is compared with the longitudinal direction. There was a problem that the anisotropy was increased and the mechanical strength was low.

On the other hand, the conventional liquid crystalline polyester film has low solubility in organic solvents, and is poor in formability for forming into a film form for the production of multilayer circuit boards for semiconductor packages, and thus is not easy to handle. Moreover, in order to raise the reliability of the board | substrate for packages, the higher heat resistance of a liquid crystal film is also calculated | required.

Japanese Patent Laid-Open No. 2004-315678 is an attempt to produce a liquid crystalline polyester film having low anisotropy, and is a liquid crystal containing a liquid crystalline polyester containing a structural unit derived from an aromatic amine derivative and an aprotic solvent. A method for producing a polyester film is described. However, the polyester film produced by this method still has low solubility in organic solvents, and the heat resistance was not sufficiently improved.

Accordingly, there is a need to develop a polyester film having a new structure that has a low anisotropy and can increase solubility in organic solvents and at the same time maintain excellent heat resistance.

1. Japanese Patent Publication No. 2004-315678

In the present invention, it is to provide a polyester resin for a semiconductor package substrate and a film prepared therefrom that are not only easy to form a film but also have excellent heat resistance because of low anisotropy and high solubility in a polar organic solvent.

In addition, the present invention is to provide a liquid crystalline polyester film for a semiconductor package substrate exhibiting low anisotropy, improved solubility, and excellent heat resistance made from a polyester resin.

In the present invention, a polyester resin obtained by reducing intermolecular interaction by introducing a fluorene group having a bulky structure into the polyester polymer chain, a resin composition comprising the same, and a semiconductor having low anisotropy, improved solubility and excellent heat resistance prepared therefrom Provided is a film for a package substrate.

According to the present invention, aromatic bulky fluorene groups may be introduced into the polyester polymer chain to increase the solubility in polar organic solvents, thereby facilitating the film manufacturing process for semiconductor package substrates.

In the present invention, a polyester resin for a highly integrated semiconductor package circuit board having low anisotropy and high heat resistance and a film prepared therefrom can be obtained. In addition, the present invention provides a resin for a semiconductor package circuit board having a high solubility in a polar organic solvent and easy to manufacture a film for a semiconductor package substrate, and a liquid crystal film prepared therefrom.

This invention relates to the polyester resin for semiconductor package substrates, The said resin is 20-50 mol% of structural units represented by following formula (1), 40-25 mol% of structural units represented by following formula (2), and a following formula It is the polyester resin which consists of 40-25 mol% of structural units represented by (3).

(1) -O-Ar1-CO-

(2) -OC-Ar2-CO-

(3) -HN-Ar3-NH-

Wherein Ar 1 is 2,6-naphthalene or 4,4′-biphenylene, preferably 2,6-naphthalene,

Ar2 is represented by the following formula (1),

<Formula 1>

Wherein R is H, CH ₃ , or CH ₂ CH ₃ , preferably R is H

Ar3 is one of the following Chemical Formulas 1-3.

<Formula 1>

Wherein R is H, CH ₃ , or CH ₂ CH ₃ , preferably R is H

<Formula 2>

<Formula 3>

When the content of the structural unit represented by the formula (1) in the resin according to the present invention exceeds 50 mol%, the solubility of the produced film is significantly lowered, and if less than 20 mol%, liquid crystallinity may not be exhibited.

In addition, when the content of the structural unit represented by the formula (2) and the structural unit represented by the formula (3) in the resin exceeds 40 mol%, the liquid crystallinity of the produced film is lowered, and when the content is less than 25 mol%, the solubility is significantly reduced. Can be. It is preferable to use substantially the same amount of the structural unit represented by Formula (2) and the structural unit represented by Formula (3).

In a preferred embodiment of the present invention, the polyester resin is represented by 30 to 40 mol% of the structural unit represented by the formula (1), 35 to 30 mol% of the structural unit represented by the formula (2), and the formula (3) It consists of 35-30 mol% of structural units.

The manufacturing method of the polyester resin which concerns on this invention is not restrict | limited, For example, the aromatic hydroxy acid corresponding to the structural unit of Formula (1), and the fluorene skeleton corresponding to the structural unit of Formula (3) were introduce | transduced. Acylation of diamines or aromatic diamines with an excess of fatty acid anhydride to obtain acylates, and by transesterification of the obtained acylates with the dicarboxylic acids of the fluorene skeleton corresponding to the structural unit of formula (2) for dissolution polymerization and the like. Can be prepared.

Another aspect of the present invention is to produce a film for a semiconductor package substrate by applying a polyester resin according to the invention on a support substrate. In this case, a film may be prepared by adding a known filler and additives to the polyester resin. Examples of the filler include organic fillers such as epoxy resin powder, melamine resin powder, urea resin powder and styrene resin powder, and inorganic fillers such as silica, alumina, titanium oxide, zirconium oxide, kaolin, calcium carbonate and calcium phosphate. Since heat resistance and linear expansion coefficient are easy to control, it is preferable to use an inorganic filler.

As the additive, one or two or more known coupling agents, antisettling agents, ultraviolet absorbers, heat stabilizers, and the like may be used.

A polyester film is prepared by dissolving a resin composition comprising a polyester resin according to the present invention, an optional component filler and / or a conventional additive in an organic solvent. The production method of the polyester film according to the present invention is not particularly limited and may be prepared according to a known method. For example, the resin composition according to the present invention is dissolved in an organic solvent, and the obtained solution composition is filtered as necessary to remove fine foreign substances, and then slurryed by adding an inorganic filler and various additives, and then on a supporting substrate, For example, the surface may be uniformly coated on the surface by a tape casting method (doctor blade method, comma coating method), roller coating method, dip coating method, spray coating method, spin coating method, curtain coating method, slot coating method, screen printing method, or the like. After coating, the solvent may be removed by heating to obtain a liquid crystalline polyester film. The tape casting method is most preferable from the viewpoint of ease of manufacturing process and size increase.

Since the resin according to the present invention has excellent solubility in various polar organic solvents such as N, N 'dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and the like, a film using an organic solvent The molding of is very easy.

It is preferable that it is 5-500 micrometers from a viewpoint of film forming property and a mechanical characteristic, and, as for the thickness of the final produced film, it is more preferable that it is 20-100 micrometers from a viewpoint of handleability.

The invention can be better understood by the following examples, which are intended to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Example  One

3 moles of 9,9-bis (4-aminophenyl) fluorene (3), 9,9-bis (4-carboxyphenyl) flu, in a reactor equipped with a stirring device, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser 3 mol of orene (2), 4 mol of 2-hydroxy-6-naphthenic acid (1), and 11 mol of acetic anhydride were added. After the reactor was sufficiently replaced with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen stream, and then refluxed for 3 hours while maintaining. Thereafter, the mixture was heated to 320 ° C. over 170 minutes while removing the by-product acetic acid and unreacted acetic anhydride, and the powder contents were taken out when the reaction time was regarded as the end of the torque. 10 g of the obtained powder was added to 90 g of N-methylpyrrolidone and heated to 120 ° C., whereby a completely dissolved solution was obtained. The solution was stirred and defoamed, coated on a copper foil with a comma coater, and then heat treated at 100 ° C. for 1 hour and 250 ° C. for 1 hour to remove the solvent, thereby obtaining a copper foil phase thermoplastic film.

Example  2

3 moles of 1,4-phenylenediamine (3), 3 moles of 9,9-bis (4-carboxyphenyl) fluorene (2) in a reactor with a stirring device, torque meter, nitrogen gas introduction tube, thermometer and reflux cooler , 4 mol of 2-hydroxy-6-naphthenic acid (1), and 11 mol of acetic anhydride were added thereto. After the reactor was sufficiently replaced with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen stream, and then refluxed for 3 hours while maintaining. Thereafter, the mixture was heated to 320 ° C. over 170 minutes while removing the by-product acetic acid and unreacted acetic anhydride, and the powder contents were taken out when the reaction time was regarded as the end of the torque. 10 g of the obtained powder was added to 90 g of N, N'-dimethylacetamide and heated to 120 ° C, whereby a completely dissolved solution was obtained. The solution was stirred and defoamed, coated on a copper foil with a comma coater, and then heat treated at 100 ° C. for 1 hour and 250 ° C. for 1 hour to remove the solvent, thereby obtaining a copper foil phase thermoplastic film.

Comparative example  One

1.5 moles of 1,4-phenylenediamine (3), 1.5 moles of 9,9-bis (4-carboxyphenyl) fluorene (2) in a reactor equipped with a stirring device, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser , 7 mol of 2-hydroxy-6-naphthenic acid (1), and 11 mol of acetic anhydride were added. After the reactor was sufficiently replaced with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen stream, and then refluxed for 3 hours while maintaining. Thereafter, the mixture was heated to 320 ° C. over 170 minutes while removing the by-product acetic acid and unreacted acetic anhydride, and the powder contents were taken out when the reaction time was regarded as the end of the torque. 5 g of the obtained powder was added to 95 g of N-methylpyrrolidone and heated to 120 ° C., and no dissolution was performed.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be regarded as being included in the scope of the present invention.

Claims (9)

Polyester resin which consists of 20-50 mol% of structural units represented by following formula (1), 40-25 mol% of structural units represented by following formula (2), and 40-25 mol% of structural units represented by following formula (3). :
(1) -O-Ar1-CO-
(2) -OC-Ar2-CO-
(3) -HN-Ar3-NH-
Wherein Ar 1 is 2,6-naphthalene or 4,4′-biphenylene,
Ar2 is represented by the following formula (1),
<Formula 1>

Ar3 is any one of the following Chemical Formulas 1-3.
<Formula 1>

<Formula 2>

<Formula 3>

(In Formula (1), R is H, CH ₃ , or CH ₂ CH ₃ ) According to claim 1, Ar1 in the formula (1) is 2,6-naphthalene, and Ar2 and Ar3 in the formula (2) and (3) each independently have a skeleton structure of Formula 1 wherein R is H Phosphorus polyester resin.
30-30 mol% of structural units represented by said Formula (1), 35-30 mol% of structural units represented by said Formula (2), and 35-30 mol of structural units represented by said Formula (3) Polyester resin which consists of%.
The polyester resin of Claim 1 in which the structural unit represented by the said Formula (2) and the structural unit represented by the said Formula (3) are contained in equal amount.
The polyester resin according to any one of claims 1 to 4, wherein the resin is used as a material of a semiconductor package substrate.
The film for semiconductor package substrates obtained by apply | coating the polyester resin of any one of Claims 1-4 on a support substrate.
The method of claim 6, wherein the film is a filler selected from silica, alumina, titanium oxide, zirconium oxide, kaolin, calcium carbonate, calcium phosphate, or a mixture thereof, and a coupling agent, an anti-settling agent, and an ultraviolet absorber in the polyester resin. A film for a semiconductor package substrate obtained by dissolving a resin composition obtained by mixing an additive selected from a thermal stabilizer or a mixture thereof in an organic solvent and applying it onto a support substrate.
8. The film for semiconductor package substrate according to claim 7, wherein the resin composition is applied onto a support substrate by a tape casting method.
The film of claim 6, wherein the film has a thickness of 5 to 500 μm.