JP2017122759A - Method for selecting adhesive assistant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for selecting an adhesive assistant by which an adhesive assistant to be used for a photosensitive resin composition can be easily selected in a short time.SOLUTION: The method for selecting an adhesive assistant aims to select an adhesive assistant of a photosensitive resin composition comprising an alkali-soluble resin, a compound that generates an acid by irradiation of active rays or a compound that generates a radical by irradiation of active rays, and an adhesive assistance, the selected adhesive assistant improving adhesiveness to a substrate. The adhesive assistant selected satisfies such conditions that: (1) when a mixture of the adhesive assistant and a material constituting a substrate, and a single state of the adhesive assistant are each measured to obtain a thermogravimetric reduction curve and a differential thermal analysis curve, the thermogravimetric reduction curve of the mixture is shifted to a higher temperature side than that of the single adhesive assistant, and the differential thermal analysis curve of the mixture has an exothermic peak or an endothermic peak that is not observed in the single adhesive assistant; and (2) when a mixture of the adhesive assistant and the alkali-soluble resin, and a single state of the adhesive assistant are each measured to obtain a thermogravimetric reduction curve and a differential thermal analysis curve, the thermogravimetric reduction curve of the mixture is shifted to a higher temperature side than that of the single adhesive assistant, and the differential thermal analysis curve of the mixture has an exothermic peak or an endothermic peak that is not observed in the single adhesive assistant.SELECTED DRAWING: None

Description

  The present invention relates to a method for selecting an adhesion assistant. More specifically, the present invention relates to a method for selecting an adhesion assistant that improves the adhesion of a cured film formed using a photosensitive resin composition to a substrate.

  Semiconductor interlayer insulating films are required to have adhesion to various substrates (substrates), and it is necessary to add adhesion aids such as silane coupling agents and nitrogen-containing heterocyclic compounds to improve the adhesion to these substrates. There is. The adhesion aid is bonded by having a chemical bond between the substrate and the adhesion aid, and between the adhesion aid and the cured film of the photosensitive resin composition, or by having strong interaction due to van der Waals force, etc. Improve sexiness.

  Since it is very difficult to determine the strength of reaction and interaction between the substrate and the adhesion aid, and between the adhesion aid and the cured film of the photosensitive resin composition, the conventional photosensitive resin composition Adhesion aid is added to the object, and the adhesion strength in the bulk state is evaluated by the stud pull method or the cross-cut method, and the adhesion aid is determined by comparing the magnitude of the adhesion strength (for example, patent document) 1).

  However, the method for evaluating the adhesion assistant of Patent Document 1 confirms the adhesive force after adding the adhesion assistant to the photosensitive resin composition, and thus it is necessary to prepare the photosensitive resin composition itself and actually Although the evaluation was made with the addition of an adhesion assistant, there were some adhesion assistants that did not contribute to the improvement of adhesion or had little effect on the improvement of adhesion. Therefore, it took time and labor to select the adhesion assistant. In addition, there are problems that it takes a long time to select an adhesion assistant, such as the fact that there are many types of adhesion assistants and the amount of addition of the adhesion assistant needs to be optimized.

JP 2014-145957 A

  An object of the present invention is to provide a method for selecting an adhesion assistant capable of simply and quickly selecting an adhesion assistant used for a photosensitive resin composition.

  There is no known method for easily determining whether an adhesion assistant having a strong effect on a specific substrate has a chemical bond to the substrate or an interaction with the resin. Moreover, there has been no evaluation means so far for a method for determining the adhesive force between the adhesion assistant layer formed on the substrate and the substrate. Therefore, when an adhesion aid is added to a specific resin composition and the effect of improving the adhesion to the substrate is not obtained, it is due to the interaction between the substrate and the adhesion aid, or The cause could not be determined whether it was due to the interaction of the photosensitive resin composition with the cured film.

  As a result of intensive research, the inventors have found that the evaluation results of the substrate material and the adhesion assistant are in close correlation with the adhesion evaluation results of the photosensitive resin composition containing the adhesion assistant, and the selection of the adhesion assistant is efficient. Found that can be done. In addition, as a result of studying a method for simply determining the progress of the reaction between the adhesion assistant and the substrate, the present inventors measured the thermogravimetric-differential thermal analysis (TG-DTA) of the adhesion assistant, thereby The present invention has been completed by ascertaining that the adhesion aid is stably present with respect to the curing temperature of the adhesive resin composition and whether the reaction with the base can proceed.

According to the present invention, the following methods for selecting an adhesion assistant and the like are provided.
1. Adhesion that improves adhesion to a substrate of a photosensitive resin composition containing an alkali-soluble resin, a compound that generates an acid upon irradiation with actinic light or a compound that generates a radical upon irradiation with actinic light, and an adhesion assistant A method for selecting an auxiliary agent,
A method for selecting an adhesion assistant that satisfies the following (1) and (2).
(1) A thermogravimetric decrease curve and a differential thermal analysis curve were measured for the mixture of the adhesion assistant and the material constituting the substrate, and the adhesion assistant alone, and the thermogravimetry curve of the mixture was the adhesion assistant. It has shifted to a higher temperature side than a single thermogravimetric loss curve, and the differential thermal analysis curve of the mixture has an exothermic peak or an endothermic peak that is not observed in the differential thermal analysis curve of the adhesion aid alone.
(2) A thermogravimetric reduction curve and a differential thermal analysis curve are measured for the mixture of the adhesion assistant and the alkali-soluble resin, and the adhesion assistant alone, and the thermogravimetric reduction curve of the mixture is obtained from the adhesion assistant alone. It has shifted to a higher temperature side than the thermogravimetric decrease curve, and the differential thermal analysis curve of the mixture has an exothermic peak or an endothermic peak that is not observed in the differential thermal analysis curve of the adhesion aid alone.
2. 2. The method for selecting an adhesion assistant according to 1, wherein the compound that generates an acid upon irradiation with active light is a diazonaphthoquinone compound.
3. The method for selecting an adhesion assistant according to 1 or 2, wherein the adhesion assistant is a silane coupling agent.
4). 3. The method for selecting an adhesion assistant according to 1 or 2, wherein the adhesion assistant is a nitrogen-containing heterocyclic compound.

  ADVANTAGE OF THE INVENTION According to this invention, the selection method of the adhesion aid which can select the adhesion aid used for the photosensitive resin composition simply and in a short time can be provided.

It is a figure which shows the thermogravimetric reduction curve in case an adhesion assistant is 3-mercaptopropyl trimethoxysilane. It is a figure which shows a differential thermal analysis curve in case an adhesion aid is 3-mercaptopro 9 pill trimethoxysilane. It is a figure which shows the thermogravimetric reduction curve in case an adhesion assistant is 3-methacryloxypropyl trimethoxysilane. It is a figure which shows a differential thermal analysis curve in case an adhesion assistant is 3-methacryloxypropyl trimethoxysilane.

  Hereinafter, the method for selecting the adhesion aid of the present invention will be described in detail. The present invention is not limited to the following embodiments.

<Selection method of adhesion aid>
The method for selecting an adhesion aid according to the present invention comprises a photosensitive resin composition comprising an alkali-soluble resin, a compound that generates an acid upon irradiation with actinic rays or a compound that generates radicals upon irradiation with an actinic ray, and an adhesion assistant. For an object, a method for selecting an adhesion assistant that improves the adhesion to a substrate, and an adhesion assistant that satisfies the following (1) and (2) is selected.
(1) A thermogravimetric reduction curve and a differential thermal analysis curve are measured for the mixture of the adhesive assistant and the material constituting the substrate, and the adhesive assistant alone, and the thermogravimetric reduction curve of the mixture is the adhesive assistant. The differential thermal analysis curve of the mixture is shifted to a higher temperature side than the single thermogravimetric loss curve, and the exothermic peak or endothermic peak is not observed in the differential thermal analysis curve of the adhesion aid alone.
(2) A thermogravimetric reduction curve and a differential thermal analysis curve were measured for the mixture of the adhesion assistant and the alkali-soluble resin, and the adhesion assistant alone, and the thermogravimetric reduction curve of the mixture was measured for the adhesion assistant alone. It has shifted to a higher temperature than the thermogravimetric loss curve, and the differential thermal analysis curve of the mixture has an exothermic peak or an endothermic peak that is not observed in the differential thermal analysis curve of the adhesion aid alone.
Note that (1) and (2) may be referred to as requirement (1) and requirement (2), respectively.
Further, in the requirements (1) and (2), “the differential thermal analysis curve of the mixture of the adhesion assistant and the material constituting the substrate or the mixture of the adhesion assistant and the alkali-soluble resin is the differential thermal analysis curve of the adhesion assistant alone. The term “having an exothermic peak or endothermic peak that is not observed in” includes a case where a peak shift indicating a reaction between the adhesion assistant and the material constituting the substrate or the alkali-soluble resin is observed.

Adhesion aids in the photosensitive resin composition are used to improve adhesion by reacting physically or chemically with the underlying silicon substrate or copper substrate in the process from drying to curing after coating. The selection criteria for the auxiliary agent include the presence or absence of reaction with the substrate that is the base.
In the method for selecting an adhesion assistant according to the present invention, a material constituting the substrate (hereinafter sometimes referred to as a substrate material), an adhesion assistant, and an alkali-soluble resin and an adhesion assistant as a base resin of the photosensitive resin composition are used. By evaluating each, the adhesion assistant of the photosensitive resin composition which can improve the adhesiveness with respect to a board | substrate can be selected.
In the method of the present invention, since it is not necessary to prepare a photosensitive resin composition, an adhesion assistant can be selected easily and in a short time compared to conventional screening methods.

The adhesion assistant contained in the photosensitive resin composition preferably forms a chemical bond with the substrate during the prebaking or curing process, or has a strong interaction with the substrate due to van der Waals force or the like.
In order to confirm this, in the present invention, the result of TG-DTA measurement (thermogravimetric-differential thermal analysis measurement) with the adhesion assistant alone, the mixture of the adhesion assistant and the substrate material, and the adhesion assistant and the alkali-soluble By comparing the results of the TG-DTA measurement of the resin mixture, it is confirmed whether or not the reaction of the adhesion assistant-substrate material or the adhesion assistant-alkali-soluble resin proceeds. Moreover, it is confirmed by TG-DTA measurement whether an adhesion aid exists stably under hardening temperature.

In order for the adhesion assistant to contribute to the adhesion to the substrate in the photosensitive resin composition, the adhesion assistant does not volatilize during the curing process, and the reaction needs to proceed with both the substrate and the alkali-soluble resin. In order to confirm volatilization during the curing process, when thermogravimetric analysis of the adhesion assistant alone is performed using TG-DTA measurement, it remains at 200 ° C., 250 ° C., 300 ° C., 350 ° C. depending on the type of adhesion assistant. There is a difference in weight.
Since the adhesion assistant needs to be bonded to the substrate-adhesion assistant-photosensitive resin composition cured film after curing, it is considered that the adhesion assistant that does not remain after curing of the photosensitive resin composition does not contribute to adhesion. That is, an adhesive aid that is effective for adhesion with a 350 ° C. photosensitive resin composition must be an adhesion aid that does not lose its weight at 350 ° C. The same applies to curing at 200, 250, and 300 ° C.
Further, when the adhesion assistant is, for example, a silane coupling agent, it has a reactive group such as a triethoxysilyl group and a trimethoxysilyl group, and ethanol, methanol, etc. are volatilized by heating, respectively. As the reaction proceeds, weight loss proceeds. Since the content of triethoxysilyl group and trimethoxysilyl group varies depending on the structure of the silane coupling agent, the degree of weight reduction varies. Therefore, for example, instead of using 1%, 3%, and 5% weight loss temperatures as indicators, it is an important indicator that weight remains at the curing temperature.

Regarding requirement (1), when a mixture of the adhesion assistant and the substrate material is measured by TG-DTA, when the adhesion assistant and the substrate material react, the thermogravimetric decrease curve of the mixture and the thermogravimetric decrease curve of the adhesion assistant alone Compared with, the thermogravimetric decrease curve of the mixture is shifted to the high temperature side, and it can be confirmed that the heat resistance is improved. Here, “shifting to a high temperature side” means that the temperature of the mixture is higher when compared at the same reduction rate in the thermogravimetric decrease curve. In addition, comparing the differential thermal analysis curve of the mixture with the differential thermal analysis curve of the adhesion assistant alone, the differential thermal analysis curve of the mixture can confirm an exothermic peak or endothermic peak that did not appear in the case of the adhesion assistant alone.
On the other hand, when the reaction does not proceed between the adhesion assistant and the substrate material, the thermogravimetric decrease curve of the mixture draws almost the same curve as the thermogravimetric decrease curve of the adhesion assistant alone. Further, the differential thermal analysis curve of the mixture draws almost the same curve as the differential thermal analysis curve of the adhesion assistant alone.
The exothermic peak or endothermic peak appearing in the differential thermal analysis curve of the mixture of the adhesion assistant and the substrate material varies depending on the reaction between the functional group of the adhesion assistant and the substrate material.

  In Requirement (1), the substrate used for the measurement may be used as it is, but it is preferably pulverized with a mortar or the like. By pulverizing the substrate material, the reaction point with the adhesion aid is increased, and the reaction between the adhesion aid and the substrate material powder easily proceeds. This makes the thermogravimetric loss and differential heat detected in the TG-DTA measurement more accurate.

Regarding requirement (2), when a mixture of an adhesion assistant and an alkali-soluble resin is measured by TG-DTA, when the adhesion assistant reacts with an alkali-soluble resin, the thermogravimetric reduction curve of the mixture and the thermogravimetric weight of the adhesion assistant alone Compared with the decrease curve, the thermogravimetric decrease curve of the mixture is shifted to the high temperature side, and it can be confirmed that the heat resistance is improved. In addition, comparing the differential thermal analysis curve of the mixture with the differential thermal analysis curve of the adhesion assistant alone, the differential thermal analysis curve of the mixture can confirm an exothermic peak or endothermic peak that did not appear in the case of the adhesion assistant alone.
On the other hand, when the reaction does not proceed between the adhesion assistant and the alkali-soluble resin, the DTA thermogravimetric decrease curve of the mixture draws almost the same curve as the DTA thermogravimetric decrease curve of the adhesion assistant alone. Further, the DTA differential thermal analysis curve of the mixture draws almost the same curve as the DTA differential thermal analysis curve of the adhesion assistant alone.
In addition, the exothermic peak or endothermic peak appearing in the DTA differential thermal analysis curve of the mixture of the adhesion assistant and the alkali-soluble resin varies depending on the reaction between the functional group of the adhesion assistant and the substrate.

<Photosensitive resin composition>
The method for selecting an adhesion assistant of the present invention includes an alkali-soluble resin (hereinafter also referred to as the component (A)), a compound that generates an acid by irradiation with actinic light, or a compound that generates a radical by irradiation with actinic light (hereinafter, (B) also referred to as a component) and an adhesion assistant (hereinafter also referred to as the component (C)) is applied to a photosensitive resin composition, and an adhesion assistant having excellent adhesion to a substrate is selected. it can.
Hereinafter, each component and board | substrate of the said photosensitive resin composition are demonstrated. However, the photosensitive resin composition and the substrate to which the method for selecting the adhesion assistant of the present invention is applied are not limited to the following.

In the present specification, “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto. Similarly, “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid”, “(meth) acrylic group” means “acrylic group” or “methacrylic group”, and “( “Meth) acryloyl” means “acryloyl” or “methacryloyl”.
Further, “A or B” only needs to include either “A” or “B”, and may be “A + B”.

“Alkali-soluble” of the alkali-soluble resin as component (A) means that it is soluble in an alkaline developer, and one criterion will be described below.
(A) A component alone or a varnish obtained by dissolving in any solvent together with the components (B) and (C) described above or later will be formed by spin coating on a substrate such as a silicon wafer. Thus, a coating film having a thickness of 5 μm is obtained. This is immersed in any one of tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution at 20 to 25 ° C. As a result, when it can be dissolved as a uniform solution, the component (A) is considered soluble in an alkaline developer.

  The component (A) preferably has a main chain skeleton having a structure of polyimide, polyoxazole or a precursor thereof. Specifically, polyimide, polyamideimide, polyoxazole, polyamide, and precursors thereof (for example, polyamic acid, polyamic acid ester, polyhydroxyamide, etc.). Among these, it is preferable to use polyimide, polyoxazole or a precursor thereof from the viewpoint of increasing the solvent resistance of the cured film.

The component (A) can be synthesized, for example, by the following method.
Polyimide can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine and dehydrating and ring-closing.
Polyamideimide can be obtained, for example, by reacting tricarboxylic acid and diamine and dehydrating and ring-closing.
Polyamide can be obtained, for example, by reacting dicarboxylic acid dichloride with diamine.
Polyamic acid (polyimide precursor) can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine.
The polyamic acid ester (polyimide precursor) can be obtained, for example, by reacting a tetracarboxylic acid diester dichloride with a diamine.
Polyhydroxyamide (polyoxazole precursor) can be obtained, for example, by reacting dicarboxylic acid dichloride and dihydroxydiamine (usually those in which an amino group and a phenolic hydroxyl group are bonded to the ortho position of the aromatic ring).
Any of the above-described methods for producing an alkali-soluble resin can be a known method. Among these alkali-soluble resins, polyhydroxyamides (polybenzoxazole precursors) that are closed by heating to become polybenzoxazoles are preferable from the viewpoint of excellent heat resistance, mechanical properties, and electrical properties.

（一般式（Ａ−１）中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す） The polyhydroxyamide preferably has a structural unit represented by the following general formula (A-1). The “amide unit containing a hydroxyl group” represented by the following general formula (A-1) is finally converted into an oxazole compound having excellent heat resistance, mechanical properties, and electrical properties by dehydration ring closure at the time of curing. .

(In general formula (A-1), U represents a tetravalent organic group, and V represents a divalent organic group.)

  The polyhydroxyamide preferably has a structural unit represented by the general formula (A-1). However, since the solubility of the polyhydroxyamide in an alkaline aqueous solution is derived from a phenolic hydroxyl group, the general formula (A-1) It is more preferable that the “amide unit containing a hydroxy group” represented by the formula is contained in a certain proportion or more. As such, polyhydroxyamide represented by the general formula (A-2) is preferable. Note that two Vs in the general formula (A-2) may be the same or different.

（一般式（Ａ−２）中、Ｕは４価の有機基を示し、ＶとＷは２価の有機基を示す。
ｊとｋはそれぞれモル分率を示し、ｊとｋの和は１００モル％であり、ｊが６０〜１００モル％、ｋが０〜４０モル％である。）

(In General Formula (A-2), U represents a tetravalent organic group, and V and W represent a divalent organic group.
j and k each represent a mole fraction, and the sum of j and k is 100 mol%, j is 60 to 100 mol%, and k is 0 to 40 mol%. )

Here, it is preferable that the molar fraction of j and k in general formula (A-2) is j = 80-100 mol% and k = 0-20 mol%.
The polyhydroxyamide having the structural unit represented by the general formula (A-2) can be generally synthesized from a dicarboxylic acid derivative, a hydroxy group-containing diamine, and, if necessary, other diamines. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamine. As the dihalide derivative, a dichloride derivative is preferable. The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. A known method can be used for these.

  In the general formula (A-2), the tetravalent organic group represented by U is preferably a tetravalent aromatic group, preferably having 6 to 40 carbon atoms, and having 6 to 40 carbon atoms. A tetravalent aromatic group is more preferable. In addition, since the tetravalent organic group represented by U is a polybenzoxazole precursor, it generally reacts with a dicarboxylic acid to form a polyamide structure “two hydroxy groups and two amino groups, respectively. It is a residue of a diamine having two sets of structures having an hydroxy group and an amino group located in the ortho position on an aromatic ring.

  Such diamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane. Bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-) 4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3- Although hexafluoropropane etc. are mentioned, it is not limited to these. These compounds can be used alone or in combination of two or more.

  In the general formula (A-2), the divalent organic group represented by W is generally a “diamine residue” that reacts with a dicarboxylic acid to form a polyamide structure, and other than the diamine that forms U. And a divalent aromatic group or aliphatic group is preferred, and those having 4 to 40 carbon atoms are preferred, and divalent aromatic groups having 4 to 40 carbon atoms are more preferred.

  Examples of such diamines include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p. -Phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4 And aromatic diamine compounds such as-(4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene. In addition to these, diamines containing silicone groups include LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C, and X-22-161E ( Any of these include, but are not limited to, Shin-Etsu Chemical Co., Ltd., trade name). These compounds can be used alone or in combination of two or more.

  In the general formula (A-2), the divalent organic group represented by V is a dicarboxylic acid residue that reacts with diamine to form a polyamide structure, and is preferably a divalent aromatic group. The number of carbon atoms is preferably 6 to 40, and a divalent aromatic group having 6 to 40 carbon atoms is more preferable from the viewpoint of heat resistance of the cured film. In addition, when V is a divalent organic group having an aliphatic straight chain structure having 6 to 30 carbon atoms, it is preferable in that sufficient physical properties can be obtained even if the temperature at the time of thermosetting is lowered to 280 ° C. or lower. .

  Examples of the dicarboxylic acid having an aromatic group include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4′-di Carboxybiphenyl, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenylpropane), 5-tert-butyl Aromatic dicarboxylic acids such as isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid and 2,6-naphthalenedicarboxylic acid; 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid An acid, 1, 3- cyclopentane dicarboxylic acid etc. are mentioned.

  Examples of the dicarboxylic acid having an aliphatic straight chain structure having 6 to 30 carbon atoms include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, and methylsuccinic acid. Acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipine Acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid Hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosandioic acid, heneicosandioic acid, docosandioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid Examples include acids, nonacosandioic acid, triacontanesandioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following general formula (A-3). Is not to be done. These compounds can be used alone or in combination of two or more.

（一般式（Ａ−３）中、Ｚは炭素数１〜６の炭化水素基であり、ｎは１〜６の整数である。）

(In general formula (A-3), Z is a C1-C6 hydrocarbon group, and n is an integer of 1-6.)

The polyimide precursor may have a carbon-carbon unsaturated double bond in the main chain skeleton. A conventionally known polyimide precursor having a monovalent organic group having a carbon-carbon unsaturated double bond can be used without particular limitation.
Among these, it is preferable to have a structure represented by the following general formula (A-4).

In formula (A-4), A is any one of tetravalent organic groups represented by the following formulas (A-5a) to (A-5d), and B is represented by the following formulas (A-6a) to (A -6c) is a divalent organic group. R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group. At least one of R ¹ and R ² is a monovalent organic group having a carbon-carbon unsaturated double bond.

（式中、Ｘ及びＹは、各々独立に、各々が結合するベンゼン環と共役しない２価の基又は単結合を示す。）

(In the formula, X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded.)

（式（Ａ−６ａ）中、Ｒ^３〜Ｒ^１０は、各々独立に水素原子、フッ素原子又は１価の有機基を表し、Ｒ^３〜Ｒ^１０の少なくとも１つはフッ素原子、メチル基又はトリフルオロメチル基を表す。
式（Ａ−６ｂ）中、Ｘは、結合するベンゼン環と共役しない２価の基又は単結合を示す。）

(In formula (A-6a), R ^{3 to} R ¹⁰ each independently represents a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ^{3 to} R ¹⁰ represents a fluorine atom, a methyl group or a trivalent group. Represents a fluoromethyl group.
In formula (A-6b), X represents a divalent group or a single bond that is not conjugated to the benzene ring to which it is bonded. )

A in the formula (A-4) is a structure derived from tetracarboxylic dianhydride used as a raw material, and is a tetravalent organic compound represented by the above formulas (A-5a) to (A-5d). One of the groups.
In X and Y, examples of the divalent group that is not conjugated to the benzene ring include an oxygen atom, a dimethylmethylene group, a bis (trifluoromethyl) methylene group, a dimethylsilylene group, and a methyltrifluoromethylmethylene group.

  Examples of the acid anhydride that gives the structure of A include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4′-biphenyltetracarboxylic dianhydride, 4 , 4′-oxydiphthalic dianhydride, thioether diphthalic anhydride, and tetracarboxylic dianhydrides represented by formula (A-7) to formula (A-13). These may be used alone or in combination of two or more.

B in the formula (A-4) is a structure derived from a diamine used as a raw material. Examples of the monovalent organic group represented by R ^{3 to} R ¹⁰ include a methyl group and a trifluoromethyl group. Examples of the divalent group that is not conjugated with the benzene ring represented by X include an oxygen atom, a dimethylmethylene group, a bis (trifluoromethyl) methylene group, a dimethylsilylene group, and a methyltrifluoromethylmethylene group.

As the diamine that gives the structure of B, it is preferable that at least one of R ^{3 to} R ¹⁰ is a fluorine atom, a methyl group, or a trifluoromethyl group, from the viewpoint of good i-line transmittance and low stress. Is preferably a fluorine atom, a methyl group or a trifluoromethyl group, more preferably two or more are a methyl group or a trifluoromethyl group.
Among these, as the diamine having the structure represented by (A-6a), it is preferable to use a diamine represented by the following formula (A-14) to formula (A-21). These may be used alone or in combination of two or more.

The monovalent organic group having a carbon-carbon unsaturated double bond is preferably an ethylenically unsaturated group, more preferably a (meth) acryloxyalkyl group having 1 to 10 carbon atoms, and a (meth) acryloxyethyl group. (Meth) acryloxypropyl group or (meth) acryloxybutyl group is more preferable.
When the component (A) has a monovalent organic group having a carbon-carbon unsaturated double bond, crosslinking between molecular chains by radical polymerization is possible in combination with a compound that generates radicals upon irradiation with actinic rays. .

R ¹ and R ^{2 in} formula (A-4) are at least one monovalent organic group having a carbon-carbon unsaturated double bond, but the other is a hydrogen atom or an alkyl having 1 to 20 carbon atoms. It may be a group or a cycloalkyl group.

There is no restriction | limiting in particular in the synthesis | combining method of the said polyimide precursor, It can synthesize | combine by a conventionally well-known method. For example, it can be synthesized by addition polymerization of tetracarboxylic dianhydride and diamine. Alternatively, the tetracarboxylic dianhydride as a raw material can be synthesized into a diester derivative, converted to an acid chloride, and condensed in the presence of a diamine and a basic compound (for example, pyridine).
Examples of the polyimide include polyimide formed from the above polyimide precursor.

(A) As for the molecular weight of a component, it is preferable that the weight average molecular weights in polystyrene conversion are 10,000-100000, It is more preferable that it is 15000-100,000, It is further more preferable that it is 20000-85000. When the weight average molecular weight is 10,000 or more, the stress after curing tends to be sufficiently reduced. When the weight average molecular weight is 100,000 or less, good solubility in a solvent tends to be obtained. In addition, the viscosity of the solution increases and the handleability is unlikely to deteriorate.
The weight average molecular weight can be measured by a gel permeation chromatography method and is determined by conversion using a standard polystyrene calibration curve.

  The component (B) is a compound that generates an acid or a radical upon irradiation with actinic rays. By reacting with light, the coating film formed using the composition has a function of solubilizing or insolubilizing the developer. It is an ingredient. The component (B) is more preferably a compound that generates an acid upon irradiation with actinic rays, and the compound generates an acid upon irradiation with actinic rays to increase the solubility of the actinic ray irradiation part in an alkaline aqueous solution. It is a compound having a function.

  Specific examples of the compound that generates an acid upon irradiation with actinic rays include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and the like. Of these, o-quinonediazide compounds such as diazonaphthoquinone compounds are preferred because of their high sensitivity.

  A conventionally well-known thing can be especially used for the said o-quinonediazide compound without a restriction | limiting. For example, an o-quinonediazide compound can be obtained by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent. Among these, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and 1-naphthoquinone-2-diazide-5 -Ester compounds obtained by reaction with sulfonyl chlorides are preferred. This is commercially available from AZ Electronic Materials (trade name “TPPA528”). Further, commercially available ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name “IRGACURE -OXE-02 "manufactured by BASF Corporation) can also be used.

  When the component (B) is a compound that generates an acid upon irradiation with actinic rays, the content of the component (B) is such that the difference in dissolution rate between the exposed portion and the unexposed portion increases, and the sensitivity becomes better. 3-100 mass parts is preferable with respect to 100 mass parts of (A) component, 5-50 mass parts is more preferable, and 5-30 mass parts is further more preferable.

  Compounds that generate radicals upon irradiation with actinic rays include oxime ester compounds; benzophenone; N, N′-tetraalkyl-4,4 such as N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone). '-Diaminobenzophenone; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, etc. Quinones fused with an aromatic ring such as alkyl anthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkyl benzoin; benzyl derivatives such as benzyldimethyl ketal

  When the component (B) is a compound that generates radicals upon irradiation with actinic rays, the content of the component (B) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A).

Examples of the component (C) include organic silane compounds and nitrogen-containing heterocyclic compounds.
Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropyltri Methoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, triethoxysilylpropylethylcarbamate, 3- (triethoxysilyl) propyl succinate Acid anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl) Butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (2-pyridylethyl) thiopropyltrimethoxysilane, 3-thiocyanatepropyltriethoxysilane, and the like.
Examples of the nitrogen-containing heterocyclic compound include benzotriazole, 1H-tetrazole, 5-aminotetrazole, 5-phenyltetrazole, and triazole.
As the adhesion assistant, the above compounds can be used alone or as a mixture of two or more.

  The content of the component (C) is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 10 mass parts.

  The photosensitive resin composition may further include the following (D) component, (E) component, (F) component, and (G) component in addition to the (A) component, (B) component, and (C) component.

The photosensitive resin composition may contain a solvent as component (D).
The solvent is preferably a polar solvent that completely dissolves the component (A) such as a polyimide precursor, such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylformamide, Dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl -2-imidazolidinone and the like. Among these, N-methyl-2-pyrrolidone is preferably used from the viewpoint of room temperature viscosity stability.
These solvents may be used alone or in combination of two or more.

  The content of the component (D) is preferably 100 to 280 parts by mass, more preferably 110 to 260 parts by mass, and 130 to 170 parts by mass with respect to 100 parts by mass of the component (A). More preferably.

The photosensitive resin composition may contain a photopolymerizable compound having an ethylenically unsaturated bond as the component (E).
Examples of the photopolymerizable compound include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, styrene, divinylbenzene, 4-vinyltoluene , 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide N, N- dimethyl acrylamide, N- methylol acrylamide. These may be used alone or in combination of two or more.

When the photosensitive resin composition contains the component (E), the content of the component (E) is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the component (A), and 3 to 75 parts by mass. Part is more preferable, and 5 to 50 parts by mass is even more preferable.
If the content of the component (E) is 1 part by mass or more, better photosensitive characteristics can be imparted, and if it is 100 parts by mass or less, the heat resistance of the cured film can be further improved.

In order to ensure good storage stability, the photosensitive resin composition may contain a radical polymerization inhibitor or a radical polymerization inhibitor as the component (F).
Examples of radical polymerization inhibitors or radical polymerization inhibitors include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, Examples thereof include N-phenyl-2-naphthylamine, cuperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, and nitrosamines. These may be used alone or in combination of two or more.

  When the photosensitive resin composition contains the component (F), the content of the component (F) is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the component (A). More preferably, the content is 0.01 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass. When the content of the component (F) is less than 0.01 parts by mass, the storage stability tends to decrease. When the content is more than 30 parts by mass, the heat resistance of the cured film formed from the photosensitive resin composition may decrease. There is.

The photosensitive resin composition may contain a thermal crosslinking agent as the component (G).
A crosslinking agent is a compound that reacts with other components such as an alkali-soluble resin to crosslink in the step of heat treatment after applying, exposing and developing the composition, or the compound itself is polymerized in the step of heat treatment. It is. As a result, good film strength can be obtained even at a relatively low temperature, for example, 200 ° C. or lower, and mechanical properties, chemical resistance, and flux resistance can be improved.

  The component (G) is not particularly limited except that it is a compound that is crosslinked or polymerized in the heat treatment step, but is preferably a compound having a methylol group, an alkoxymethyl group, an epoxy group, or a vinyl ether group in the molecule. Among them, compounds having two or more methylol groups and alkoxymethyl groups in the molecule are more preferable in that they are excellent in sensitivity and varnish stability and can prevent melting of the film when the film is cured after pattern formation.

（式（Ｇ−１）中、複数のＲ^１５及びＲ^１６は、各々独立に水素原子又は一価の有機基である。
２つのＲ^１６は、互いが結合することで環構造となっていてもよい。なお、Ｒ^１５及びＲ^１６が複数存在する場合、複数のＲ^１５及び複数のＲ^１６は各々同一でも異なっていてもよい。） The component (G) preferably contains a compound represented by the following formula (G-1).

(In the formula (G-1), R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a monovalent organic group.
Two R ¹⁶ may be a ring structure by one another binds. When a plurality of R ¹⁵ and R ¹⁶ are present, the plurality of R ¹⁵ and the plurality of R ¹⁶ may be the same or different. )

（式中、Ｒ^１７は各々独立に炭素数１〜２０のアルキル基である。Ｒ^１８は各々独立に炭素数１〜１０のアルキル基である。なお、複数のＲ^１７及び複数のＲ^１８は各々同一でも異なっていてもよい。） Examples of the compound represented by the formula (G-1) include compounds having a structure represented by the following formula. However, the compound represented by the formula (G-1) is not limited thereto.

(Wherein R ¹⁷ is each independently an alkyl group having 1 to 20 carbon atoms. R ¹⁸ is each independently an alkyl group having 1 to 10 carbon atoms. Note that a plurality of R ¹⁷ and a plurality of R ¹⁸ are Each may be the same or different.)

  Examples of the substrate on which the photosensitive resin composition is applied include a silicon wafer, a metal substrate, and a ceramic substrate.

<Method for producing patterned cured film>
The said photosensitive composition is suitable for manufacture of a pattern cured film. The produced pattern cured film can be used as an interlayer insulating film layer, a surface protective film layer or the like of an electronic component.
A method for producing a patterned cured film includes a step of applying and drying the above-described photosensitive resin composition on a substrate to form a coating film, a step of irradiating the coating film with an actinic ray and exposing it to a pattern, It includes a step of removing the exposed portion by development to obtain a pattern resin film, and a step of heat-treating the pattern resin film.
Hereinafter, each step will be described.

Application can be performed by dipping, spraying, screen printing, spin coating, or the like.
When the above composition is applied, dried, and formed into a film, the film thickness is preferably 3 to 20 μm, more preferably 5 to 15 μm. The heat drying during film formation is preferably from 80 to 160 ° C, more preferably from 100 to 160 ° C. The heat drying time is preferably 60 to 300 seconds, more preferably 90 to 210 seconds.

  The solvent is removed by heating by drying. Examples of the apparatus include a hot plate and an oven. The heating temperature for removing the solvent by heating is preferably 80 to 150 ° C., and the heating time is preferably 60 seconds to 300 seconds. By removing the solvent by heating, a non-adhesive coating film can be formed.

As the active light to be irradiated, ultraviolet rays such as i rays, far ultraviolet rays, visible rays, electron beams, X-rays and the like can be used. i-line is most preferred.
The pattern exposure is not particularly limited, but is preferably performed through a mask on which a desired pattern is drawn.

  The developer is not particularly limited, but flame retardant solvents such as 1,1,1-trichloroethane, alkali aqueous solutions such as aqueous sodium carbonate and tetramethylammonium hydroxide, N, N-dimethylformamide, dimethyl sulfoxide, Good solvents such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates, etc., and these good solvents and poor solvents such as lower alcohols, water, and aromatic hydrocarbons A mixed solvent or the like is used.

The development temperature is preferably 20 to 25 ° C. Usually, it is 23 degreeC, for example. The development time is preferably set as 1.5 to 2.5 times the time required for the coating film formed from the photosensitive resin composition to be immersed in the developer and completely dissolved. It is more preferable to set 2 times as the development time.
By developing and removing the unexposed portions by development, a desired pattern resin film can be obtained. After development, rinsing with a poor solvent or the like may be performed as necessary.

  The conditions for the heat treatment of the pattern resin film are, for example, 80 to 400 ° C. and 5 to 300 minutes. Thereby, imidization can be advanced and the pattern cured film containing a polyimide can be obtained. When the polyimide is used after curing, the chemical resistance and heat resistance of the pattern cured film can be improved.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to these Examples.
Component (A) used in the composition was prepared by the following method.
[Preparation of component (A)]
Synthesis example 1
In a 0.5 liter flask equipped with a stirrer and a thermometer, 195.6 g of pyromellitic acid-hydroxyethyl methacrylate diester (PMDA (HEMA)) solution and 4,4′-oxydiphthalic acid-hydroxyethyl methacrylate diester (ODPA ( 58.7 g of HEMA)) solution was added, and then 25.9 g (217.8 mmol) of thionyl chloride was added dropwise using an addition funnel while maintaining the reaction solution temperature at 10 ° C. or lower under ice cooling. After the addition of thionyl chloride was completed, the reaction was carried out for 2 hours under ice cooling to obtain a solution of PMDA (HEMA) and ODPA (HEMA) acid chloride. Then, using a dropping funnel, 21.7 '(99.0 mmol) of 2,2'-bis (trifluoromethyl) benzidine, 34.5 g (435.6 mmol) of pyridine, 0.076 g (0.693 mmol) of hydroquinone -90.2 g of methylpyrrolidone solution was added dropwise while cooling with ice so that the temperature of the reaction solution did not exceed 10 ° C. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester. This was polymer A1 (pyromellitic acid-hydroxyethyl methacrylate diester / 4,4′-oxydiphthalic acid-hydroxyethyl methacrylate diester / 2,2′-bis (trifluoromethyl) benzidine condensation polymer (PMDA / ODPA / TFMB)). And
The weight average molecular weight calculated | required by standard polystyrene conversion of the obtained polymer A1 was 34,000.

The measurement conditions of the weight average molecular weight calculated | required by GPC method standard polystyrene conversion of polymer A1 are as follows, Solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio) with respect to 0.5 mg of polymers. )] Measured using 1 mL of solution Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min
Detector: UV270nm

Synthesis example 2
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g (60 mmol) of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged, and after the flask was cooled to 5 ° C., thionyl chloride was added. 23.9 g (120 mmol) was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid chloride. Next, 87.5 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 18.30 g (50 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and m -After 2.18 g (20 mmol) of aminophenol was stirred and dissolved, 9.48 g (120 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C, a solution of 4,4'-diphenyl ether dicarboxylic acid chloride was added for 30 minutes. After dropwise addition, stirring was continued for 30 minutes. Next, the solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain a hydroxyl-terminated polyhydroxyamide (hereinafter referred to as polymer A2).
The weight average molecular weight of the obtained polymer A2 obtained by GPC standard styrene conversion was 23400, and the degree of dispersion was 1.8.

The following components were prepared as the component (B), component (C), component (D) and component (E) of the composition.
(B) Component B1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE-OXE-02, BASF (Made by Co., Ltd.)
B2: 1-naphthoquinone-2-diazide-5-sulfonic acid of 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane Ester (Esterification rate of about 90%, TPPA528, manufactured by AZ Electronic Materials)

(C) Component C1: 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.)
C2: 3-glycidoxypropyltriethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
C3: 3-Ureidopropyltriethoxysilane (KBE-585, manufactured by Shin-Etsu Chemical Co., Ltd.)
C4: Bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane (SIB1140.0, manufactured by Gerest)
C5: 2- (2-pyridylethyl) thiopropyltrimethoxysilane (SIP-6926, manufactured by Gerest)
C6: 3-thiocyanate propyl triethoxysilane (SIT-7908, manufactured by Gerest)
C7: Phenyltrimethoxysilane (KBM-103, Shin-Etsu Chemical Co., Ltd.)
C8: Methyltrimethoxysilane (SZ6070, Toray Dow Corning Co., Ltd.)
C9: 3-methacryloxypropyltrimethoxysilane (SZ6030, Toray Dow Corning Co., Ltd.)
C10: Benzotriazole (Wako Pure Chemical Industries, Ltd.)
C11: 1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

(D) Component D1: N-methylformamide (Wako Pure Chemical Industries, Ltd.)
D2: γ-butyrolactone (Wako Pure Chemical Industries, Ltd.)

(E) Component E1: Triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

Example 1-14 and Comparative Example 1-8
[Evaluation of heat resistance and reactivity]
About (C) component, heat resistance and reactivity were evaluated based on the following method. The results are shown in Tables 1 and 2.

(1) Heat resistance evaluation (C) 20 mg of the component was weighed in an aluminum pan, and 10 ° C./min in a temperature range of 30 ° C. to 450 ° C. in an air atmosphere using a thermogravimetric analyzer SA6300 (manufactured by SII). The temperature was raised and the weight loss curve and differential thermal analysis curve were measured to evaluate the heat resistance.

(2) Confirmation of reaction with silicon After weighing 20 mg of powder obtained by pulverizing a Si substrate using a mortar into an aluminum pan, 20 mg of component (C) was weighed into an aluminum pan containing Si powder and heated. Using a gravimetric analyzer SA6300 (manufactured by SII), the temperature was increased at 10 ° C./min in an air atmosphere at a temperature range of 30 ° C. to 450 ° C., and a weight reduction curve and a differential thermal analysis curve were measured. The reactivity of was evaluated.
Here, the evaluation of reactivity is made by comparing the thermogravimetric decrease curve of the component (C) alone with the thermogravimetric decrease curve of the component (C) and the silicon powder. ) Shifted to a higher temperature than the thermogravimetric decrease curve of the component alone, and in the differential thermal analysis curve of the component (C) and the silicon powder, there was an exothermic peak or endothermic peak that was not observed in the (C) component single measurement. When observed, it was evaluated as “◯”. On the other hand, the thermogravimetric decrease curve of the component (C) alone and the thermogravimetric decrease curve of the component (C) and the silicon powder were compared, and the thermogravimetric decrease curve was not substantially changed. C) The case where no exothermic peak or endothermic peak was observed in the component single measurement was evaluated as “x”.

(3) Confirmation of reaction with copper After weighing 20 mg of copper powder (manufactured by Tokyo Chemical Industry Co., Ltd.) into an aluminum pan, 20 mg of component (C) was weighed into an aluminum pan containing copper powder and thermogravimetric. Using an analyzer SA6300 (manufactured by SII), the temperature was raised at 10 ° C./min in an air atmosphere at a temperature range of 30 ° C. to 450 ° C., and a thermogravimetric decrease curve and a differential thermal analysis curve were measured. The reactivity of was evaluated.
Here, the evaluation of reactivity is made by comparing the thermogravimetric decrease curve of the component (C) alone with the thermogravimetric decrease curve of the component (C) and the copper powder. ) The thermogravimetric decrease curve of the component alone is shifted to a higher temperature side, and in the differential thermal analysis curve of the component (C) and the copper powder, there is an exothermic peak or endothermic peak that was not observed in the (C) component alone measurement. When observed, it was evaluated as “◯”. On the other hand, the thermogravimetric decrease curve of the component (C) alone and the thermogravimetric decrease curve of the component (C) and the copper powder were compared. C) The case where no exothermic peak or endothermic peak was observed in the component single measurement was evaluated as “x”.

  FIG. 1 is a thermogravimetric decrease curve when the component (C) is C1. From the thermogravimetric decrease curve shown in FIG. 1, it can be seen that the thermogravimetric decrease curve is shifted to the high temperature side by adding Si or Cu powder, especially when Cu powder is added. As a result, it is considered that C1 reacted with Si and copper, and the heat resistance was improved.

  FIG. 2 is a differential thermal analysis curve when the component (C) is C1. In the differential thermal analysis curve shown in FIG. 2, C1 shows an exothermic reaction at around 60 ° C., which is not observed in a single measurement in the presence of copper, whereas the endothermic reaction slightly shifts to a lower temperature in the presence of Si. It can be seen that some reaction of C1 proceeds between Si and Cu.

  From the literature regarding the silane coupling agent, it is considered that when trimethoxysilane or triethoxysilane reacts with the substrate, methanol or ethanol volatilizes, so that an endothermic reaction occurs. Therefore, it is considered that the reaction between C1 and Si proceeds from the reaction between the trimethoxysilyl group and Si. On the other hand, it is considered that the reaction between the mercapto group and copper proceeds because the exothermic reaction proceeds due to the reaction of C1 with copper. Thus, the information of the functional group reacting with the substrate can be obtained from the TG-DTA measurement, which is very useful.

  FIG. 3 is a TG curve when the component (C) is C9. The thermogravimetric decrease curve when C9 and Si powder shown in FIG. 3 are added is almost the same as that of C-9 alone, indicating that the reaction between C9 and Si powder does not proceed. The thermogravimetric decrease curves of C9 and Cu powder are slightly improved. Therefore, it shows that the reaction between C9 and Cu powder proceeds.

  FIG. 4 is a differential thermal analysis curve when the component (C) is C9. Comparing the DTA curves for C9 alone, C9 and Si powder, and C9 and Cu powder shown in FIG. 4, there is almost no difference in the endothermic peak around 180 ° C. compared to C-9 alone for C9 and Si powder. It is considered that the reaction between C9 and Si does not proceed. However, in the case of Cu powder, since the peak top of the endothermic peak is slightly shifted to the high temperature side, some reaction may occur between C9 and Cu.

(4) Confirmation of reaction with base resin (component (A)) After polymer A1 synthesized in Synthesis Example 1 was weighed on an aluminum pan, 20 mg of component (C) was weighed on an aluminum pan and subjected to thermogravimetric analysis. Using an apparatus SA6300 (manufactured by SII), the temperature was raised at 10 ° C./min in an air atmosphere at a temperature range of 30 ° C. to 450 ° C., and a thermogravimetric decrease curve and differential heat (TG) curve were measured. The reactivity with the resin was evaluated. Further, the reactivity was similarly evaluated using the polymer A2 synthesized in Synthesis Example 2 instead of the polymer A1.
Here, the evaluation of reactivity is made by comparing the thermogravimetric decrease curve of the component (C) alone with the thermogravimetric decrease (TG) curve of the component (C) and the base resin, and the thermogravimetric decrease curve of the component (C) and the base resin. Is shifted to a higher temperature side than the thermogravimetric decrease curve of component (C) alone, and in the differential thermal analysis (DTA) curve of component (C) and the base resin, it was not observed in the measurement of component (C) alone A case where an exothermic peak or an endothermic peak was observed was evaluated as “◯”. On the other hand, the thermogravimetric decrease curve of the component (C) alone and the thermogravimetric decrease curve of the component (C) and the base resin were compared, and the thermogravimetric decrease curve was almost unchanged, and the differential thermal analysis (DTA) curve. The case where no exothermic peak or endothermic peak was observed in the component (C) single measurement was evaluated as “x”.

[Evaluation of adhesion]
Using the adhesion assistants of Example 1-14 and Comparative Example 1-8, the compositions of the combination pattern (a) and the combination pattern (b) shown in Table 3 were prepared, and the adhesion was evaluated by the following method. . The results are shown in Tables 1 and 2.

The prepared composition was spin coated on a Si substrate (silicon wafer) and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 11 to 12 μm. Using a vertical diffusion furnace (trade name “μ-TF”, manufactured by Koyo Thermo System Co., Ltd.), the substrate provided with this resin film is heated to 270 ° C. in the case of the composition of the combination pattern (a) in nitrogen. In the case of the composition of the combination pattern (b), the coating film was heat-treated (cured) at 230 ° C. (temperature raising time 1.5 hours) for 2 hours to form a film on the Si substrate. A cured film having a thickness of about 10 μm was obtained.
A cured film was obtained on the Cu substrate in the same manner as described above except that a Cu substrate was used instead of the Si substrate. The Cu substrate is a substrate obtained by forming a TiN film on a silicon substrate by sputtering, forming a copper film on the TiN film by sputtering, and performing copper plating using the copper film as a seed layer.

The resulting cured film was cut into 10 × 10 grids with a razor using a cross cut guide (manufactured by Cortec Co., Ltd.), and the cured film was divided into 100 small pieces. After sticking an adhesive tape (made by Nichiban Co., Ltd.) there, it was peeled off. When peeling the adhesive tape, the adhesion was evaluated as follows according to the number of small pieces peeled from the substrate.
○: No peeling remaining 100
Δ: Remaining 60-99
×: 59 or less remaining

From the above results, in order to obtain a photosensitive resin composition having good adhesion to the Si substrate or Cu substrate, regardless of the material used for preparing the composition, it interacts with each of Si, Cu and alkali-soluble resin. If it chooses from the adhesion | attachment adjuvant which has, it has a correlation with the adhesive evaluation result of the photosensitive resin composition in a tape test, and can select an adhesion | attachment adjuvant efficiently.
On the other hand, when selecting an adhesion assistant without knowledge of the present invention, all the adhesion assistants C1 to C9 are blended with respect to one composition, and not only the cross-cut method but also the stud pull method or the like is evaluated. It is necessary to determine the effect of the adhesion assistant by combining the results. For example, when the skeleton of the alkali-soluble resin (A) is changed, it is necessary to examine all the adhesion assistants again, and it takes a very long time to select the adhesion assistant.

Claims (4)

Adhesion that improves adhesion to a substrate of a photosensitive resin composition containing an alkali-soluble resin, a compound that generates an acid upon irradiation with actinic light or a compound that generates a radical upon irradiation with actinic light, and an adhesion assistant A method for selecting an auxiliary agent,
A method for selecting an adhesion assistant that satisfies the following (1) and (2).
(1) A thermogravimetric decrease curve and a differential thermal analysis curve were measured for the mixture of the adhesion assistant and the material constituting the substrate, and the adhesion assistant alone, and the thermogravimetry curve of the mixture was the adhesion assistant. It has shifted to a higher temperature side than a single thermogravimetric loss curve, and the differential thermal analysis curve of the mixture has an exothermic peak or an endothermic peak that is not observed in the differential thermal analysis curve of the adhesion aid alone.
(2) A thermogravimetric reduction curve and a differential thermal analysis curve are measured for the mixture of the adhesion assistant and the alkali-soluble resin, and the adhesion assistant alone, and the thermogravimetric reduction curve of the mixture is obtained from the adhesion assistant alone. It has shifted to a higher temperature side than the thermogravimetric decrease curve, and the differential thermal analysis curve of the mixture has an exothermic peak or an endothermic peak that is not observed in the differential thermal analysis curve of the adhesion aid alone.   The method for selecting an adhesion promoter according to claim 1, wherein the compound that generates an acid upon irradiation with actinic rays is a diazonaphthoquinone compound.   The method for selecting an adhesion assistant according to claim 1 or 2, wherein the adhesion assistant is a silane coupling agent.   The method for selecting an adhesion assistant according to claim 1 or 2, wherein the adhesion assistant is a nitrogen-containing heterocyclic compound.

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