TECHNICAL FIELD

The present invention relates to a resin containing a specific structure. More specifically, this invention relates to a resin suited for applications such as a surface protective film or interlayer insulating film of an electronic component or circuit board, a solder resist for a circuit board, an insulating layer of an organic electroluminescent element, a flattening film of a driving thin film transistor substrate of a display device using an organic electroluminescent element, an interlayer insulating film of a thin film transistor, an on-chip microlens of a solid-state image pickup element, various displays, and a flattening film for a solid state image pickup device, and a photosensitive resin composition using the resin.

This invention further relates to 5,5′-dihydroxyl-4,4′-diaminobiphenyl derivatives which can be used for these resins, resin compositions and pharmaceutical intermediates, a process for producing the same, and a method for synthesizing dibromobiphenyl derivatives used therein.

BACKGROUND ART

Resins having excellent insulating characteristics and made of organic polymers are applied to a flattening film of a driving thin film transistor substrate of a display device using a surface protective film or an interlayer insulating film of an electronic part or circuit board, an insulating layer of an organic electroluminescent element, and the organic electroluminescent element. Polyimide resins and polybenzoxazole resins which are particularly excellent in heat resistance, chemical resistance, mechanical properties and the like have been widely used.

In recent years, with the miniaturization and thinning of a device, deterioration of the process yield due to warpage of a device substrate and adverse effect on the reliability of the device are concerned. For this reason, it is also required to impart resins with the property of reducing the warpage of the substrate.

Examples of a method for reducing the warpage of the device substrate include a method of reducing a difference in coefficient of linear thermal expansion between a resin film-formed on the substrate and the substrate itself to reduce stress produced by a difference in thermal expansion. Since the linear thermal expansion coefficient of ordinary resins is larger by 10 ppm or more than the linear thermal expansion coefficient of a substrate, it is effective to reduce the linear thermal expansion coefficient of the resin in order to reduce the stress. In order to attain this object, polyimide resins including a rigid structure in the main chain and having a small linear thermal expansion coefficient (see, for example, Patent Documents 1 to 6), polyimide-polybenzoxazole resins (see, for example, Patent Document 7) and the like have been reported.

In a resin film formed using the resin, it is necessary to form a pattern such as a through hole in an opening of an electrode portion or the like. In the prior art, a pattern has been formed by forming a positive type photoresist film or the like on a resin film having no photosensitivity and etching the film. However, with this method, it is difficult to miniaturize the pattern due to high density and high speed and large capacity of a device, and therefore, resins having photosensitivity have been studied.

For example, regarding a positive type photosensitive resin composition, a composition containing a polyamide acid ester containing a phenolic hydroxyl group and an o-quinonediazide compound (see, for example, Patent Document 8), a composition containing a solvent-soluble ring-closing-type polyimide and naphthoquinonediazide compound (see, for example, Patent Document 9), and a composition containing a polybenzoxazole precursor and a naphthoquinonediazide compound (see, for example, Patent Document 10) have been reported. Regarding a negative type photosensitive resin composition, a polyimide precursor in which an acrylic compound is bonded to a side chain (see, for example, Patent Document 11) and a mixture of polyimide with an acrylic compound (see, for example, Patent Document 12) have been reported.

In addition, monomers for synthesizing these polyimides have a very important role in the performance of a polyimide polymer. A monomer of polyimide mainly has two kinds of monomers including a diamine monomer and a diacid anhydride monomer. When structures of the two kinds of monomers are changed, it is possible to remarkably improve the performance in each field of polyimide, such as the coefficient of thermal expansion, light transmittance, or elastic modulus. As a result of study, it is disclosed that introducing a hydroxyl group into a monomer can remarkably change the coefficient of thermal expansion, light transmittance or modulus of elasticity of polyimide (see, for example, Non-Patent Document 1). In an industrial production process, in order to reduce the cost of a polymer monomer, it is very important to obtain a low-cost hydroxyl group-containing diamine monomer. On the other hand, 4,4′-diaminobiphenyl derivative monomers have already been widely used for the synthesis of polyimides, and the cost is very low (see, for example, Patent Documents 13 and 14).

A dibromobiphenyl derivative used for this is a commonly used chemical raw material, pharmaceutical intermediate, or electronic material. At the same time, since a bromine group in a dibromobiphenyl compound can be further converted into a hydroxyl group, an amino group, a cyano group, an alkoxy group, a double bond, a triple bond, an organometallic compound, or etc., the bromine group finds very wide application in the fields of refinement, polymer intermediates, and the like. Commonly used methods for synthesizing dibromobiphenyl derivatives are as follows. That is, a biphenyl compound is used as a raw material, and a dibromobiphenyl derivative can be obtained under the action of a bromination reagent. However, there is a possibility that a plurality of positions on a benzene ring of a biphenyl derivative are substituted with bromine, and selectivity is poor, so that the yield of reaction is low. In order to solve this problem, a bromination reaction using liquid bromine and protic solvent ethanol alone is disclosed (see, for example, Patent Document 15). It is also disclosed to promote the reaction by using liquid bromine as a bromination reagent and acetic acid as a solvent and adding sodium acetate (see, for example, Non-Patent Document 2).

PRIOR ART DOCUMENTS

Patent Documents

Patent Document 1: Japanese Patent Laid-open Publication No. H2-283762Patent Document 2: Japanese Patent Laid-open Publication No. H8-48773Patent Document 3: Japanese Patent Laid-open Publication No. H8-253584Patent Document 4: Japanese Patent Laid-open Publication No. H11-158279Patent Document 5: Japanese Patent Laid-open Publication No. 2002-363283Patent Document 6: Japanese Patent Laid-open Publication No. 2003-212996Patent Document 7: Japanese Patent Laid-open Publication No. 2007-177117Patent Document 8: Japanese Patent Laid-open Publication No. H4-204945Patent Document 9: Japanese Patent Laid-open Publication No. H3-209478Patent Document 10: International Publication No. WO10/092824Patent Document 11: Japanese Patent Laid-open Publication No. 2011-191749Patent Document 12: International Publication No. WO04/109403Patent Document 13: Japanese Patent Laid-open Publication No. 2007-106859Patent Document 14: U.S. Pat. No. 5,378,420Patent Document 15: Chinese Patent Application Publication No. 200780002686.6

Non-Patent Documents

Non-Patent Document 1: Progress in Polymer Science (2012), 37(7), 907-974Non-Patent Document 2: Synthesis, 2000, 383-388

SUMMARY OF THE INVENTION

Problems to be Solved by the Invention

However, in the above resin having a small linear thermal expansion coefficient, there is a problem that due to the rigid skeleton introduced into the main chain, the absorbance, particularly the absorbance of an i-line (light having a wavelength of 365 nm) currently widely used for pattern processing a photosensitive resin, is high, and it is difficult to impart good photosensitive characteristics due to energy loss caused by absorption of the resin itself.

A further object is to produce, as a monomer for synthesizing polyimide, a low-cost hydroxyl group-containing diamine monomer in which a hydroxyl group is introduced into a 4,4′-diaminobiphenyl derivative monomer.

Further, regarding a dibromobiphenyl derivative used for this, the yield is very low according to the method disclosed in Patent Document 15, and there is a problem that it is not suitable for mass production. Furthermore, according to the method disclosed in Non-Patent Document 2, the degree of corrosion to equipment is relatively large due to use of acidic solvent and salt, recovery of solvent is difficult, difficulty in post-treatment is increased, and there is a problem of environmental pollution.

In view of the above-described problems of the prior art, an object of the present invention is to provide a resin having a small linear thermal expansion coefficient and a low absorbance.

A further object is to provide a production process including highly selectively introducing a bromine atom into a 5,5′-dihydroxyl-4,4′-diaminobiphenyl derivative used in these resins and a 5,5′ position, at the same time, simplifying a process for post-treating a bromination reaction, obtaining a 5,5′-dibromo-4,4′-diaminobiphenyl derivative, and then converting the bromine atom into a hydroxyl group by a reaction of an oxazole ring and a ring opening reaction. A furthermore object is to provide a method for synthesizing dibromobiphenyl derivatives used for this, easily achieving high yield, low cost, and mass production, and hardly polluting the environment.

Solutions to the Problems

As a result of intensive studies to solve the above problems, the inventors have found the present invention. That is, the present invention is a resin characterized by including at least one structure selected from the structures represented by the following general formulae (1) and (2).


(The general formula (1) is a divalent organic group, and R1and R2each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. R3and R4each represent an organic group selected from a hydroxyl group, a carboxyl group and a sulfonic acid group. X1is a single bond, O, S, NH, SO2, CO or a divalent organic group having 1 to 3 carbon atoms or a divalent crosslinked structure formed by linking two or more of them. n1is 0 or 1. When n1=0, a1is an integer of 1 to 3, b1is an integer of 1 to 3, and a1+b1is an integer of 2 to 4. When n1=1, a1is an integer of 1 to 4, b1is an integer of 0 to 3, a2is an integer of 0 to 4, b2is an integer of 0 to 4, a1+b1is an integer of 1 to 4, a2+b2is an integer of 0 to 4, and at least one of b1and b2is an integer of 1 or more.)


(The general formula (2) is a trivalent or tetravalent organic group, and R5and R6each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. R7and R8each represent an organic group selected from a hydroxyl group, a carboxyl group and a sulfonic acid group. X2is a single bond, O, S, NH, SO2, CO or a divalent organic group having 1 to 3 carbon atoms or a divalent crosslinked structure formed by linking two or more of these. a3, a4, b3and b4are integers of 0 to 3, a3+b3is an integer of 0 to 3, a4+b4is an integer of 0 to 3, at least one of a3and a4is an integer of 1 or more, and at least one of b3and b4is an integer of 1 or more. m1and m2are integers of 0 or 1, and m1+m2is an integer of 1 or 2.)

Effects of the Invention

According to the present invention, it is possible to obtain a resin having a low linear thermal expansion coefficient and a low absorbance.

