JP2006119271A - Adhesion improver and substrate treating liquid using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesion improver which does not cause deterioration of photosensitive property and improves adhesive property to a base material after heat curing. <P>SOLUTION: The adhesion improver comprises a compound selected from compounds each obtained by reacting a specific aromatic amine with a specific silane compound having a group which reacts with an aromatic amino group. A surface treating liquid for a substrate using the adhesion improver is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an adhesion improver that improves the adhesion of a resin composition, and is particularly suitable for a heat-resistant resin precursor composition used for an interlayer insulating film, a surface protective layer, etc. in the semiconductor field, and an inorganic material such as silicon. It is related with the adhesive improvement agent which improves the adhesiveness.

A heat-resistant resin such as polyimide is used for a surface protective film, an interlayer insulating film, and the like of a semiconductor element such as an LSI because of its excellent heat resistance and electrical insulation. In such an application, it is important to show high adhesiveness with a silicon substrate as a substrate material. However, the polyimide resin itself has low adhesiveness, and adhesion improvement using a silane coupling agent (see Patent Document 1), a method of improving adhesion by copolymerizing siloxane diamine to polyimide (see Patent Document 2), and the like are known. Yes.
On the other hand, with the recent miniaturization of semiconductor elements, it has become necessary to form a fine pattern of about 1 μm on polyimide. There are positive photosensitive polyimide and polybenzoxazole (see Patent Document 3) that can form a fine pattern. However, although the positive photosensitive polyimide disclosed in Patent Document 3 can form a fine pattern, the aminosilane-based silane coupling agent, which has been considered effective in the past, is used as a positive photosensitive agent. The decomposition of the naphthoquinonediazide compound promotes the degradation of sensitivity and destabilization.

So far, as an adhesion improving component used in the photosensitive composition, an imidazole silane-based component (see Patent Document 4), a component containing a partial hydrolysis condensate of an alkoxysilane compound having a nitrogen-containing group (see Patent Document 5), Particularly known as adhesion improvers for positive photosensitive resin compositions are those obtained by reacting an aminosilane compound and an acid (see Patent Document 6), and silane coupling agents in which an acroyl group is bonded to the amino group of aminosilane. (See Patent Document 7).
However, imidazole silane compounds have strong basicity, promote the decomposition of naphthoquinone diazide compounds, promote the imidation of polyimide polymers, and have poor storage stability. The addition of a compound obtained by reacting an aminosilane compound and an acid has a problem that the effect of promoting the decomposition of the naphthoquinonediazide compound is weak, but the effect of improving the adhesion is not sufficient. The silane coupling agent in which an acryloyl group is bonded to the amino group of aminosilane is photopolymerized because the acryloyl group is photopolymerized. Therefore, when making a positive photosensitive composition, the acryloyl group is photopolymerized to prevent dissolution of the exposed area. There was a problem that sensitivity was lowered.
JP 63-27834 A (Claim 3) JP-A-61-176630 (Claims 1 to 5) JP 2003-345019 A (Claims 1 to 8) JP 2004-144946 A (Claim 1) Japanese Unexamined Patent Publication No. 2004-69962 (Claims 1 to 4) JP-A-11-242338 (Claim 1) JP-A-5-25219 (Claims 1 and 2)

  The present invention is a novel compound that improves adhesion while using an acid generator such as an o-quinonediazide compound that has been used in the past, which is effective for ensuring the maintenance of photosensitive characteristics. It is an object of the present invention to provide an adhesion improver and a substrate processing solution that have good adhesive properties with a base material after heat-curing without causing a decrease in sensitivity.

  That is, this invention is an adhesion | attachment improving agent characterized by having at least 1 sort (s) of the compound represented by General formula (1)-(3).

(R ¹ , R ⁷ , R ¹¹ , R ¹² , R ¹³ are each an organic group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, an amino group, a carboxyl group, 2 to 10 carbon atoms. R ² , R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹⁰ , R ¹⁷ , R ¹⁸ , R ¹⁹ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁵ , R ⁶ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ²⁰ are each a group selected from an alkenyl group, a phenyl group, and a substituted phenyl group, each having 1 to 6 carbon atoms, an alkenyl group, A group selected from a phenyl group, a substituted phenyl group, and an alkoxy group having 1 to 6 carbon atoms, at least one of which is an alkoxy group having 1 to 6 carbon atoms, X is an alkyl group having 1 to 10 carbon atoms, alkylene Group, nitro group, hydroxyl group Represents a group selected from an alkoxy group, a carboxyl group, an ester group having 2 to 10 carbon atoms, and an amide group having 2 to 10 carbon atoms, XX and YY are single bonds,

Represents a group selected from R ²¹ and R ²² each represent a group selected from hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, an alkoxy group, a phenyl group, and a substituted phenyl group. p, q, s, u, v are integers of 1-4, m is an integer of 1-3, l is an integer of 0-2, a, b, k, n are integers of 0-10, d, f and g are integers from 1 to 4, t and h are integers from 0 to 100, and j is an integer from 1 to 3.

  The compounds represented by the general formulas (1) to (3) are aromatic by reacting a silane coupling agent having an epoxy group or a chloromethyl group, which is a group that reacts with an aromatic amine and an amino group. A compound having adhesiveness to the substrate can be obtained without reducing the activity of the amine and promoting the decomposition of the naphthoquinonediazide compound. The silanol group on the surface of the silicon substrate and the secondary amino group in the compound represented by the general formula (1) act at a low temperature of 50 to 200 ° C., and further exist in the compound represented by the general formula (1). The alkoxy group can form a siloxane bond with a silanol group on the surface of the silicon substrate, but the bond is promoted by the catalytic action of the secondary amino group in the compound represented by the general formula (1). With the above configuration, the adhesive force with the silicon substrate is further increased. In addition, since silicon nitride, silicon oxide, ceramics and the like similarly act on the surface silanol groups as the silicon-based substrate surface, the same effect can be obtained. Further, even on a metal surface such as iron, nickel, copper, etc., it acts with the OH group (hydroxyl group) formed in the thin layer of the metal oxide formed on the surface, so that good adhesion can be obtained.

R ¹ and R ⁷ each represents a group selected from an organic group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, an amino group, a carboxyl group, and an ester group having 2 to 10 carbon atoms. R ² , R ³ , R ⁴ , R ⁸ , R ⁹ , and R ¹⁰ each represent a group selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, a phenyl group, and a substituted phenyl group. R ⁵ , R ⁶ , and R ²⁰ each represent an organic group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, a phenyl group, a substituted phenyl group, and an alkoxyl group having 1 to 6 carbon atoms. Is an alkoxy group having 1 to 6 carbon atoms. X represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a nitro group, a hydroxyl group, an alkoxyl group, a carboxyl group, an ester group having 2 to 10 carbon atoms, and an amide group having 2 to 10 carbon atoms. . p and q are integers of 1 to 4, m is an integer of 1 to 3, l is an integer of 0 to 2, and k and n are integers of 0 to 10.
R ¹ and R ⁷ are a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, a fluorinated alkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a perfluoropropyl group, or a perfluorobutyl group. Groups, hydroxyl groups, nitro groups, carboxyl groups, amino groups, ester groups having 2 to 10 carbon atoms, amide groups having 2 to 10 carbon atoms, and the like. Among these, an alkyl group, a fluorinated alkyl group, and a hydroxyl group are preferable.
R ² , R ³ , R ⁴ , R ⁸ , R ⁹ , and R ¹⁰ represent a group selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a substituted phenyl group. Group, propyl group, phenyl group and the like are preferable. R ⁵ , R ⁶ , and R ²⁰ each represent an organic group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, a phenyl group, a substituted phenyl group, and an alkoxyl group having 1 to 6 carbon atoms. Represents an alkoxy group having 1 to 6 carbon atoms, and represents a methyl group, an ethyl group, a propyl group, a phenyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. It is necessary to be an alkoxyl group such as a group, a propoxy group, or a butoxy group. X represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a nitro group, a hydroxyl group, an alkoxyl group, a carboxyl group, an ester group having 2 to 10 carbon atoms, particularly a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, An alkoxyl group such as a butoxy group and a nitro group are preferred.

  As the aromatic amine that can be used in the present invention, an aromatic amine having a pKa (dissociation constant in an aqueous solution) in the range of 3 to 9 can be used. When the pKa is smaller than 3, the adhesion to the substrate is lowered, and when the pKa is larger than 9, the decomposition of the photosensitive component is promoted. More preferably, the pKa is in the range of 4-8. Examples of such amines having a pKa in the range of 3 to 9 include aniline, cyanoaniline, hydroxylaniline, nitroaniline, chloroaniline, ethyl aminobenzoate, trifluoromethylaniline, methylaniline, dimethylaniline, methylhydroxylaniline, Aromatic amines such as aminopyridine, methylaminopyridine, dihydroxyaniline and hydroxyaminopyridine, or aromatics such as diaminobenzene, triaminobenzene, diaminopyridine, triaminopyridine, hydroxydiaminobenzene and dihydroxydiaminobenzene Polyvalent amines can be mentioned.

  These aromatic amines are reacted with a silane coupling agent having a group that reacts with an amino group. Preferred examples of the group that reacts with these amino groups include an epoxy group and a chloromethyl group. However, if the group that reacts with the amino group of the aromatic amine is a carboxyl group or a sulfonic acid group, the basicity of the amino group is completely lost and sometimes acts as an acid. From the above, examples of such silane compounds include trimethoxy-1-dimethylene chloride, trimethoxyepoxysilane, triethoxyepoxysilane, carboxylpropyltrimethoxysilane, bis (epoxy) tetramethoxydisiloxane, tris ( Examples thereof include silane compounds having a group that reacts with an epoxy group such as (epoxy) trimethoxydisiloxane and tris (epoxy) penta (methoxy) trisiloxane, and an amino group such as a chloromethyl group.

  The compound represented by the general formula (2) is obtained by reacting an aromatic amino compound having two or more amino groups with a silane coupling agent having a group that reacts with the amino group of the aromatic amino compound. Can be obtained.

R ¹¹ represents a group selected from an organic group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, an amino group, a carboxyl group, and an ester group having 2 to 10 carbon atoms. R ¹⁷ , R ¹⁸ , and R ¹⁹ each represent a group selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, a phenyl group, and a substituted phenyl group. R ¹⁴ , R ¹⁵ , R ¹⁶ and R ²⁰ each represent a group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, a phenyl group, a substituted phenyl group, and an alkoxyl group having 1 to 6 carbon atoms, One is an alkoxy group having 1 to 6 carbon atoms. X represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a nitro group, a hydroxyl group, an alkoxyl group, a carboxyl group, an ester group having 2 to 10 carbon atoms, and an amide group having 2 to 10 carbon atoms. . XX is a single bond,

Represents a group selected from s is an integer of 1 to 4, a and b are integers of 0 to 10, d is an integer of 1 to 4, and t is an integer of 1 to 100. R ²¹ and R ²² represent hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, an alkoxyl group, a phenyl group, or a substituted phenyl group. j represents an integer from 1 to 3.

  Aromatic diamines are those having two amino groups and having a pKa of 3 to 9, including phenylenediamine, methylphenylenediamine, cyanophenylenediamine, hydroxyphenylenediamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminobiphenyl. , Dimethyldiaminobiphenyl, dimethoxydiaminobiphenyl, bis (trifluoromethyl) diaminobiphenyl, bis (aminophenoxy) benzene, bis (aminohydroxyphenyl) propane, bis (aminophenyl) dipropylbenzene, bis (aminophenoxy) diphenyl ether, bis (Aminophenoxy) diphenylsulfone, bis (aminophenoxy) diphenylpropane, bis (aminohydroxyphenyl) hexafluoropropane It can be exemplified bis (amino-hydroxyphenyl) propane, bis (amino-hydroxyphenyl) sulfone, bis substituted, such as (aminophenoxy phenyl) ether, or an aromatic diamine which is unsubstituted. In particular, it is preferable to use a diamine having a phenolic hydroxyl group.

  Moreover, as an aromatic amino compound having two or more amino groups, tri (aminophenyl) methane, tri (aminophenyl) ethane, tri (aminophenyl) propane, tetra (aminophenyl) methane, tri (aminophenyl) Examples thereof include trifluoroethane, triamino compounds having a substituent such as a nitro group, an ester group, and an alkyl group attached thereto, and tetraamino compounds such as tetra (aminophenyl) methane.

  As the silane compound that can be used to obtain the compound represented by the general formula (2), the same silane compound as that used in the general formula (1) can be preferably used.

  The compound represented by the general formula (3) is obtained by reacting an aromatic diamine, a triamine, or a triamine or higher polyamine with a silane coupling agent having a group that reacts with an amino group having these amine compounds. Can be obtained.

R ¹² and R ¹³ each represents a group selected from an organic group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, an amino group, a carboxyl group, and an ester group having 2 to 10 carbon atoms. The substituent and the like according to Q are the same as described above. YY is a single bond,

Represents a group selected from R ²¹ and R ²² represent hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, an alkoxyl group, a phenyl group, or a substituted phenyl group. u and v are integers of 1 to 4, a and b are integers of 0 to 10, f and g are integers of 1 to 4, h is an integer of 1 to 100, and j is an integer of 1 to 3. Represents.

  In the present invention, X is selected from alkyl groups having 1 to 10 carbon atoms, alkylene groups, nitro groups, hydroxyl groups, alkoxy groups, carboxyl groups, ester groups having 2 to 10 carbon atoms, and amide groups having 2 to 10 carbon atoms. Of these, polar nitro groups, hydroxyl groups, carboxyl groups, ester groups and amide groups are preferred, and hydroxyl groups are more preferred.

  Preferable specific examples shown in the general formulas (1) to (3) include, but are not limited to, compounds shown below.

  The adhesion improver of the present invention can be obtained by reacting an aromatic amine and a silane coupling agent as they are or in a solvent and reacting in the range of −20 ° C. to 150 ° C. for 1 minute to 1 week. At this time, the compounding ratio of the aromatic amine and the silane coupling agent is preferably in the range of 10 to 400 mol%, more preferably 50 to 200 mol, with respect to the total amino group amount of 100 mol%. %. More preferably, it is the range of 60-150 mol%. If the silane coupling agent is less than 10 mol% with respect to 100 mol% of the aromatic amine, an adhesion improving effect cannot be obtained, and if it exceeds 400 mol%, a reaction such as gelation occurs and the system becomes unstable. Although the reaction can be stopped at a low temperature or for a short time, the storage stability is poor. Moreover, also when a solvent is not added, stability of a reaction material may worsen and it is preferable to make it react as a 1-90% solution.

  Further, organic acids having 1 to 10 carbon atoms such as formic acid, acetic acid and oxalic acid, acid compounds such as sulfuric acid, hydrochloric acid and phosphoric acid, or amines having 1 to 10 carbon atoms such as triethylamine and pyridine, sodium hydroxide, hydroxylated Bases such as potassium and sodium carbonate may be added as a catalyst. These catalysts are preferably used in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the aromatic amine and the silane compound.

  From solubility and stability of the obtained adhesion improver, alcohols having 1 to 7 carbon atoms, esters having 2 to 20 carbon atoms, ketones having 3 to 20 carbon atoms, and 3 to 20 carbon atoms It is possible to dilute using at least one selected from the following amides and sulfur-containing solvents having 3 to 20 carbon atoms. By diluting with these solvents, the stability of the solution can be increased. The amount of such a solvent is preferably 1 to 10,000 parts by weight with respect to 100 parts by weight of the compounds of the general formulas (1) to (3). More preferably, it is 10 parts to 1000 parts. If the amount is less than 1 part, the added effect is not observed. If the amount is more than 100000 parts, the amount of the solution added to the varnish increases, and the non-volatile content of the varnish and the decrease in the viscosity increase. Specifically, alcohols such as ethanol, propanol, butanol and methoxymethylbutanol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate and propylene carbonate, ethers such as propylene glycol monomethyl ether and tetrahydrofuran, N- Examples thereof include methyl-2-pyrrolidone, dimethylacetamide, dimethylimidazoline, and dimethyl sulfoxide.

  Further, the adhesion improver in the present invention is a surface treatment of the substrate before applying each resin composition such as photoresist, non-photosensitive polyimide, photosensitive polyimide, photosensitive polybenzoxazole, photosensitive acrylic composition to the substrate. And can be used as a treatment liquid for improving adhesiveness. In this case, a 0.0001% to 50% solution of the adhesion improver of the present invention is thinly applied to the entire substrate by a technique such as spin coating, spray coating, or roll coating. Thereafter, heat treatment is performed at a temperature of 50 to 800 ° C. for 10 seconds to 1 hour. The heat treatment may be performed in an oven or a furnace, or may be performed on a hot plate. At this time, in order to advance reaction, it can also implement in the atmosphere with a water | moisture content.

  Furthermore, the adhesion improver obtained in the present invention is 0.1 to 10 with respect to 100 parts of resin content in photoresist, photosensitive acrylic composition, non-photosensitive polyimide, photosensitive polyimide, photosensitive polybenzoxazole and the like. You may mix a weight part. By mixing, the adhesion between the photoresist, the photosensitive acrylic composition, and the photosensitive polyimide and the substrate can be improved.

  The adhesion improver obtained in the present invention precipitates a polymer precipitate even when added to a photoresist using a resin having poor solubility, a non-photosensitive polyimide solution, a photosensitive polyimide solution, a photosensitive polybenzoxazole solution, or the like. This eliminates the risk of being removed, and a solution with less foreign matter can be obtained. As the solvent used in such a solution, any solvent can be used as long as it dissolves the adhesion improver and each resin composition in addition to the solvents listed above, but the boiling point is 80 ° C to 300 ° C. Those having a boiling point of 110 ° C. to 210 ° C. are more preferable. These solvents may be used alone or in combination of two or more.

  As a photoresist, it can use preferably for the thing which added the naphthoquinone diazide sulfonic acid ester compound to the novolak resin, and the thing which added the photo-acid generator to the resin in which the alkali-soluble group was protected.

  Examples of the photosensitive acrylic composition include those obtained by adding a naphthoquinone diazide sulfonic acid ester compound to an alkali-soluble acrylic resin copolymerized with acrylic acid, those obtained by adding a photopolymerization initiator to an acrylic resin into which a photopolymerizable group has been introduced, alkali The thing which mix | blended the photopolymerizable monomer and the photoinitiator with the soluble acrylic resin can be mention | raise | lifted.

  As the photosensitive polyimide, a photopolymerizable alcohol is introduced into the carboxyl group of the polyamic acid which is a polyimide precursor by an ester bond, a photopolymerizable amine is introduced by an ion bond with the carboxyl group of the polyamic acid, Polyamide acid and naphthoquinone diazide sulfonic acid ester compound mixed, alkali-soluble polyimide and naphthoquinone diazide sulfonic acid ester compound mixed, polyamic acid ester and naphthoquinone diazide introduced with hydroxymethylphenol into the carboxyl group of the polyamic acid There are a mixture of a sulfonic acid ester compound and a naphthoquinonediazidesulfonylamidated polyimide precursor. Apart from this, it can also be applied to a photosensitive polybenzoxazole precursor composition. Examples of such a material include a polybenzoxazole precursor mixed with a naphthoquinone diazide sulfonic acid ester compound, and a polybenzoxazole precursor into which a photopolymerizable group has been introduced mixed with a photopolymerization initiator.

  As the substrate used in the present invention, a silicon substrate or a substrate having silicon oxide or silicon nitride formed on the surface thereof, such as copper, aluminum, stainless steel, chromium, nickel, palladium, or gold can be used as the substrate. Such a substrate can also be used after improving the coating property of the solution by performing oxygen plasma treatment, argon sputtering treatment, nitrogen plasma treatment or the like before applying the solution.

First, the evaluation methods used in the examples are described.
1) Evaluation of adhesion to substrate First, varnish was spin-coated on a silicon wafer, then baked for 3 minutes on a hot plate at 120 ° C (using SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.), and finally A pre-baked film having a thickness of 8 μm was produced. This film was put into an oven and cured at 170 ° C. for 30 minutes and then at 300 ° C. for 1 hour to obtain a cured film. Cure was performed in nitrogen. The cured film was cut into 10 rows and 10 columns at 2 mm intervals and subjected to a 200-hour pressure cooker test (hereinafter referred to as PCT, EHS-221MD manufactured by Tabai Co., Ltd.). Later, the adhesive properties were evaluated based on how many squares of 100 squares were peeled off by peeling with cello tape (registered trademark) (manufactured by Nichiban Co., Ltd.). In the peeling test, the number of peeling was less than 10 as good and 10 or more as bad. The PCT treatment was performed under a saturation condition of 121 ° C. and 0.21 MPa.

2) Evaluation of photosensitive properties For varnishes A to F, varnish was spin-coated on a 6-inch silicon wafer and then baked for 3 minutes on a hot plate at 120 ° C (using SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) Finally, a prebaked film having a thickness of 8 μm was produced. The film was exposed at 25 mJ / cm ² steps by the exposure amount of 0~800mJ / cm ² using an i-line stepper (GCA manufactured DSW-8000), after exposure, 2.38% tetramethylammonium (TMAH) Development was carried out with an aqueous solution (ELM-D, manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 90 seconds, followed by rinsing with pure water.

For varnishes G and H, varnish was spin-coated on a 6-inch silicon wafer, and then baked for 1 minute 30 seconds on a hot plate at 100 ° C. (using SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) Thus, a pre-baked film having a thickness of 1.5 μm was prepared. The film was exposed at 10 mJ / cm ² steps by the exposure amount of 0~500mJ / cm ² using an i-line stepper (GCA manufactured DSW-8000), after exposure, 2.38% TMAH aqueous solution for varnish G (Mitsubishi Gas Chemical Co., Ltd., ELM-D) developed for 90 seconds, and then rinsed with pure water. Varnish H was rinsed with pure water after developing for 90 seconds with a 0.4% TMAH aqueous solution.

The obtained pattern was observed with a microscope, and the minimum exposure amount Eth (1) necessary for pattern formation was estimated. Next, this heat-resistant resin precursor varnish was allowed to stand at 23 ° C. for 3 days, and the same evaluation as described above was performed to estimate the minimum exposure amount Eth (2). Next, a value of Eth (2) −Eth (1) was calculated. If the absolute value of this value was 50 mJ / cm ² or less, it was judged good, and if it exceeded 50 mJ / cm ² , it was judged as bad.
Furthermore, the pattern in which the line and space of the developed wafer was 1: 1 was observed, and how many μm of the pattern remained was observed. It is preferable that fine numbers remain, and those that remain only 30 μm or more were judged to be defective.

Synthesis Example 1 Synthesis of Hydroxyl Group-Containing Acid Anhydride Under a dry nitrogen stream, 28.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Clariant, hereinafter referred to as 6FAP) 05 mol) and 34.2 g of allyl glycidyl ether (0.3 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 100 g of ethyl acetate (manufactured by Nacalai Tesque) and cooled to -15 ° C. Here, 22.1 g of trimellitic anhydride chloride (0.11 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50 g of ethyl acetate (manufactured by Nacalai Tesque Co., Ltd.) is used so that the temperature of the reaction solution does not exceed 0 ° C. It was dripped in. After completion of dropping, the reaction was carried out at 0 ° C. for 4 hours. The yellow solid precipitated after the reaction was collected by filtration and washed with toluene (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain the following acid anhydride. The material obtained did not have a clear melting point up to 350 ° C.

Synthesis Example 2 Synthesis of Hydroxyl Group-Containing Diamine Compound 18.3 g (0.05 mol) of 6FAP in 100 mL of acetone (manufactured by Nacalai Tesque), 17.4 g of propylene oxide (0.3 mol, Tokyo Chemical Industry Co., Ltd.) And cooled to -15 ° C. A solution prepared by dissolving 20.4 g of 3-nitrobenzoyl chloride (0.11 mol, Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated yellow solid was collected by filtration and washed with methanol (manufactured by Nacalai Tesque). This solid was dissolved in 300 mL of ethylene glycol monomethyl ether (manufactured by Nacalai Tesque) and 300 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. And stirred vigorously. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 4 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the catalyst was filtered to remove the palladium compound, and the mixture was concentrated by a rotary evaporator to obtain the following diamine compound. The melting point of this product was 310 ° C. The obtained solid was used for the reaction as it was.

Synthesis example 3
Under a dry nitrogen stream, 36.6 g (0.1 mol) of 6FAP was dissolved in 100 mL of N, N-dimethylacetamide (manufactured by Wako Pure Chemical Industries, Ltd.) and cooled to -5 ° C. To this, 52.8 g of glycidyl methyl ether (0.6 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and 29.5 g of diphenyl ether dicarboxylic acid chloride (0.1 mol, manufactured by Nippon Agricultural Chemicals Co., Ltd.) was added to 50 g of acetone. The dissolved solution was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropwise addition, the temperature of the solution was raised to 10 ° C. and stirring was continued for 1 hour, and then stirring was continued at 20 ° C. for 6 hours. After stirring, the solution was poured into 10 L of water to obtain a polyhydroxyamide precipitate. After further washing with 3 L of water, the precipitate was collected by filtration and then dried in a vacuum dryer at 60 ° C. for 20 hours. 10 g of this dried polyhydroxyamide (polybenzoxazole precursor) solid and 4NT-300 as orthonaphthoquinonediazide sulfonic acid ester (1,2,4 with respect to 1 mol of 2,3,4,4′-tetrahydroxyvinzophenone) -2 g of ester obtained by reacting 3 mol of naphthoquinone-2-diazide-5-sulfonyl chloride, manufactured by Toyo Gosei Co., Ltd. in 20 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd., GBL) Photosensitive polybenzoxazole precursor varnish A was obtained.

Synthesis example 4
18.3 g (0.05 mol) of 6FAP was dissolved in 150 mL of ethanol (manufactured by Nacalai Tesque) and cooled to 5 ° C. To this, 11.2 g of potassium-t-butoxide (0.1 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added. Further, 21.8 g of t-butyl dicarbonate (0.1 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added, and stirring was continued for 2 hours. A diamine compound in which the hydroxyl group of 6FAP was protected with a t-butoxycarbonyl group Got. This solution was poured into 1 l of water to obtain a precipitate. This precipitate was collected by filtration and dried in a vacuum dryer at 30 ° C. for 20 hours.

  Under a dry nitrogen stream, 27.5 g (0.075 mol) of 6FAP and 13.4 g (0.025 mol) of diamine in which the hydroxyl group of 6FAP synthesized above was protected with a t-butoxycarbonyl group were added to N, N-dimethylacetamide. Dissolve in 150 mL and cool to -5 ° C. A solution prepared by adding 52.8 g (0.6 mol) of glycidyl methyl ether and dissolving 20.3 g of isophthalic acid dichloride (0.1 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 g of acetone was added to the reaction solution. The solution was added dropwise so that the temperature did not exceed 0 ° C. After completion of the dropwise addition, the temperature of the solution was raised to 10 ° C., and stirring was continued for 1 hour, followed by stirring at 20 ° C. for 6 hours. After stirring, the solution was poured into 10 L of water to obtain a polyhydroxyamide precipitate. This precipitate was collected by filtration and then dried for 20 hours in a vacuum dryer at 60 ° C. 10 g of this dried polyhydroxyamide (polybenzoxazole precursor) solid, 0.5 g of NAI-105 (manufactured by Midori Kagaku Co., Ltd.) as a photoacid generator, and 2 g of 4NT-300 are dissolved in 20 g of GBL. A varnish B of a functional polybenzoxazole precursor was obtained.

Synthesis example 5
Under a nitrogen stream, 20.0 g of 4,4′-diaminodiphenyl ether (0.1 mol, Wakayama Seika Kogyo Co., Ltd.) was dissolved in 350 g of GBL in a 1 L four-necked flask. The acid anhydride 71.4g (0.1 mol) synthesize | combined in the synthesis example 1 was added here with GBL40g, and it was made to react at 20 degreeC for 1 hour, and then was made to react at 40 degreeC for 2 hours. Further, 23.8 g (0.2 mol, manufactured by Mitsubishi Rayon Co., Ltd.) of N, N-dimethylformamide dimethyl acetal was added, and the mixture was stirred at 40 ° C. for 2 hours and cooled to room temperature. Thereafter, 60 g of acetic acid (1 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at room temperature for 1 hour. This was poured into 10 L of water, and the precipitate was filtered off and dried at 70 ° C. for 120 hours to obtain the desired polymer. 35 g of the obtained polymer was dissolved in 65 g of GBL, and 7.5 g of o-quinonediazide compound 4NT-300 was added thereto to obtain a varnish C as a photosensitive polyimide precursor.

Synthesis Example 6
Under a dry nitrogen stream, 24.2 g (0.04 mol) of the diamine compound synthesized in Synthesis Example 2 was dissolved in 100 g of NMP in a 1 L four-necked flask, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid 12.4 g (0.04 mol) of anhydride was added and stirred at 80 ° C. for 3 hours. Further, 8.8 g (0.06 mol) of N, N-dimethylformamide diethyl acetal was added, stirred at 40 ° C. for 2 hours, and cooled to room temperature. Thereafter, 24 g (0.4 mol) of acetic acid was added and stirred at room temperature for 1 hour. This was poured into 5 L of water, the precipitate was filtered off, and dried at 70 ° C. for 120 hours to obtain the desired polymer. 35 g of the obtained polymer was dissolved in 65 g of GBL, and 7.5 g of o-quinonediazide compound 4NT-300 used in Synthesis Example 3 was mixed therewith to obtain a photosensitive polyimide precursor varnish D.

Synthesis example 7
In a 500 mL four-necked flask under a dry nitrogen stream, 31 g (0.1 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 26 g of hydroxyethyl methacrylate (0.2 mol, Tokyo Kasei ( Co., Ltd.), 10 g of pyridine and 100 mL of GBL were added and reacted at 30 ° C. for 12 hours. After this time, the solution was cooled to -5 ° C.

  Subsequently, 41.2 g (0.2 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) of dicyclohexylcarbodiimide was dissolved in 50 mL of gamma butylactone under a dry nitrogen stream. The dicyclocarbodiimide solution was added dropwise to the cooled solution over 20 minutes. Thereafter, white precipitate was formed, but stirring was performed as it was.

  To this solution, 20 g (0.1 mol) of 4,4'-diaminodiphenyl ether was added as a solid. Thereafter, stirring was continued for 4 hours while maintaining the temperature at 0 to 5 ° C. Thereafter, the temperature of the solution was gradually returned to room temperature and further stirred for 1 hour. The obtained solution was filtered to remove a white solid, the filtrate was poured into 5 L of water, and the precipitate was collected and washed, and then dried under reduced pressure.

  30 g of solid polymer dried under reduced pressure, 0.9 g of Irgacure 369 (manufactured by Ciba Specialty Chemical) as a photopolymerization initiator, 3 g of ethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 30 g of ethyl lactate (Musashino Chemical) It was made to stir-dissolve in EL made from Co., Ltd., and the varnish E of the photosensitive polyimide precursor was obtained.

Synthesis example 8
18.3 g of 6FAP (0.05 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 g (0.05 mol) of 4,4′-diaminodiphenyl ether were dissolved in 150 mL of NMP and 50 mL of toluene at 50 ° C. To this was added 19.6 g of cyclobutanetetracarboxylic dianhydride (0.1 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1 hour at 50 ° C., and then a condenser was attached to the outside of the system to azeotrope water with toluene. While removing, the temperature of the solution was raised to 120 ° C. for 2 hours and further at 180 ° C. for 2 hours. After completion of the reaction, 30 mL of this solution was taken and 2 g of 4NT-300 was added to obtain a varnish F of photosensitive polyimide.

Synthesis Example 9
In a 500 mL three-necked separable flask equipped with a stirrer and a thermometer, 75 g of m-cresol (0.69 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 25 g of p-cresol (0.23 mol, Tokyo Chemical Industry Co., Ltd.) Made). To this, 70 g of a 37 wt% aqueous formaldehyde solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.04 g of oxalic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added. While stirring, the mixture was placed in an oil bath and heated to 100 ° C., and stirring was continued for 10 hours. Thereafter, the thermometer was removed, the internal pressure was reduced to 3990 Pa to remove water, and then heated to 180 ° C. to remove unreacted substances for 1 hour. Then, it cooled to room temperature and obtained novolak resin.

  20 g of this novolak resin, 5 g of 4NT-300, 0.1 g of trimethoxyvinylsilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003) as a naphthoquinone diazide compound, 75 g of propylene glycol monomethyl ether acetate (manufactured by Kuraray Co., Ltd., PGMEA) And varnish G was obtained by filtration through a membrane filter made of polytetrafluoroethylene having a diameter of 0.22 μm.

Synthesis Example 10
200 g of propylene glycol monomethyl ether (manufactured by Kuraray Co., Ltd., PGME) was placed in a 500 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a dropping funnel, and the temperature of the solution was 85 ° C. Here, 30 g of styrene (manufactured by Tokyo Chemical Industry Co., Ltd., 0.29 mol), 30 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd., 0.35 mol), 40 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., 0.4 Mol) was diluted with 100 g of PGME and added dropwise over 2 hours. After completion of the dropping, the temperature of the solution was raised to 95 ° C., and 0.5 g of azoisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in 5 portions every 30 minutes. Thereafter, the solution temperature was raised to 95 ° C. and stirred for 1 hour and 30 minutes, and the solution was lowered to room temperature.

  100 g of this solution was mixed with 0.1 g of KBM-1003 and 7.5 g of 4NT-300 as a naphthoquinonediazide compound, and filtered through a 0.22 μm membrane filter to obtain varnish H.

Example 1 (Synthesis of adhesion improver A1)
In a 200 mL four-necked flask, 10.9 g (0.1 mol) of 3-aminophenol was taken, and 100 g of ethyl lactate was added thereto. Next, 23.6 g of 3-glycidoxypropyltrimethoxysilane (0.1 mol, KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to this solution and stirred at 60 ° C. for 3 hours to obtain an adhesion improver A1. Obtained.

  1 g of the obtained compound solution was dissolved in 100 g of propylene glycol monomethyl ether acetate (PGMEA, manufactured by Kuraray Co., Ltd.), applied to a 6-inch wafer at 3000 rpm, and then treated with a 250 ° C. hot pouch for 1 minute.

After the treatment, the photosensitive property of varnish B was evaluated, and the change in exposure amount was 25 mJ / cm ² . This development pattern remained as a 10 μm pattern. Further, in the evaluation of adhesion to the substrate, no peeling was observed, and excellent adhesion was shown.

Further, regarding the varnish G and the varnish H, when the photosensitivity was evaluated using the wafer subjected to the above treatment, the change in exposure amount was 0 mJ / cm ² . A pattern of 2 μm remained for varnish G and 10 μm for varnish H. Regarding the adhesion to the substrate, the curing temperature was changed from 300 ° C. in the above evaluation method to 230 ° C. for varnish G and 250 ° C. for varnish H. One peel and good results.

Example 2 (Adhesion improver B1 synthesis)
36.6 g (0.1 mol) of 6FAP was added to 100 g of EL. Next, 55.6 g (0.2 mol, KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.) of 3-glycidoxypropyltriethoxysilane was added to this solution, and the mixture was stirred at 50 ° C. for 6 hours to obtain an adhesion improver B1. It was. 1 g of the resulting compound solution was added to 30 g of varnish A.

As a result of evaluating the photosensitivity of the obtained varnish, the sensitivity change was 0 mJ / cm ² , and a pattern of 5 μm was also resolved. Moreover, peeling with respect to the adhesiveness with a board | substrate was not seen.

Example 3 (Synthesis of adhesion improver A2)
16.1 g of 2-trifluoroaniline (0.1 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50 g of propylene glycol monomethyl ether. Thereafter, 24.8 g of 3-glycidoxypropylmethyldiethoxysilane (0.1 mol, KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred at 80 ° C. for 2 hours to obtain an adhesion improver A2. . Then, as in Example 2, 1 g of a solution of adhesion improver A2 was added to 30 g of varnish C.

In the evaluation of the photosensitivity of the obtained varnish, the sensitivity change was 25 mJ / cm ² , and a pattern of 10 μm remained. Moreover, peeling was not seen by the adhesiveness with a board | substrate. There was no peeling with respect to the adhesion to the substrate.

Example 4 (Synthesis of adhesion improver B2)
28 g of bis (3-amino-4-hydroxyphenyl) sulfone (0.1 mol, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 30 g of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation), and 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane 36.9 g (0.15 mol, KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred at 70 ° C. for 4 hours to obtain an adhesion improver B2. .

In the same manner as in Example 1, 1 g of the solution of the adhesion improving agent B2 was dissolved in 100 g of PGMEA, and the surface of the wafer was processed. Patterning was performed on this wafer using varnish D, but a pattern of 10 μm remained. Furthermore, there was no peeling in evaluation of the adhesiveness with a board | substrate. The change in sensitivity was 0 mJ / cm ² .

Example 5 (Synthesis of adhesion improver C1)
As an aromatic polyamine, 9.5 g of M-1540 (manufactured by Daito Sangyo Co., Ltd., active H equivalent 95 g / eq) was dissolved in 30 g of N-methyl-2-pyrrolidone, and cyclohexylepoxysilane (0.33 mol, KBM- 600, manufactured by Shin-Etsu Chemical Co., Ltd.) and stirred at 40 ° C. for 8 hours to obtain an adhesion improver C1.

In the same manner as in Example 2, 1 g of the adhesion improver C1 solution was dissolved in 30 g of varnish E. Patterning was performed using this solution, but a 10 μm pattern remained. There was no peeling with respect to the adhesion to the substrate. The change in sensitivity was 25 mJ / cm ² .

Example 6 (Synthesis of adhesion improver B3)
28 g of bis (3-amino-4-hydroxyphenyl) sulfone (0.1 mol, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 30 g of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation), and KBE- 403 was added and stirred at 70 ° C. for 4 hours to obtain an adhesion improver B3.

In the same manner as in Example 1, 1 g of the solution of the adhesion improving agent B3 was dissolved in 100 g of PGMEA, and the wafer was processed. Patterning was performed using varnish F on this wafer, but a pattern of 20 μm remained. Furthermore, there was no peeling in evaluation of the adhesiveness with a board | substrate. The change in sensitivity was 0 mJ / cm ² .

Example 7
The same procedure as in Example 2 was performed, except that a non-alkaline glass (Corning, “1787”) of 150 mm × 150 mm × 0.7 mm (thickness) was used as the substrate in Example 2. The change in sensitivity was 0 mJ / cm ² , and the pattern remained up to 15 μm. There was also no peeling off from the substrate.

Example 8
The same procedure as in Example 4 was performed except that a stainless steel substrate (“SUS304 H-TA” manufactured by Nippon Steel Corporation) was used as the substrate in Example 4 from a silicon wafer to 150 mm × 150 mm × 25 μm (thickness). The change in sensitivity was 0 mJ / cm ² , and the pattern remained up to 10 μm. There was also no peeling off from the substrate.

Comparative Examples 1-5
The same procedure as in Examples 1 to 5 was performed except that no adhesion improver was used in Examples 1 to 5 or the wafer surface treatment was not performed. In the evaluation of photosensitivity, patterns of 50 μm or more remained in varnishes B to E. For varnish A, a pattern of 20 μm, for varnish G of 10 μm, and for varnish H of 30 μm remained. Change in sensitivity 25 mJ / cm ² with a varnish B, Varnish A, C, D, E, G, was 0 mJ / cm ² with H. In the evaluation of adhesion to the substrate, peeling was observed in the cured film.

Comparative Example 6
In Example 2, 1 g of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603) was added as an adhesion improver in place of the adhesion improver B1. The adhesiveness with the substrate was not peeled off, but the sensitivity of the resin composition left for 2 days was greatly reduced by 200 mJ / cm ² from the initial stage.

Comparative Example 7
In Example 2, 1 g of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573) was added as an adhesion improving agent instead of the adhesion improving agent B1. As for the adhesion to the substrate, 30 pieces were peeled out of 100 pieces.

Comparative Example 8
In Example 3, instead of the adhesion improving agent A2, 1 g of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903) was added as an adhesion improving agent to the varnish. Regarding the adhesion to the substrate, there was no peeling, but in the evaluation of photosensitivity, there was a large decrease in sensitivity of 300 mJ / cm ^2, and a pattern of 50 μm or more remained.

Comparative Example 9
In Example 4, instead of the adhesion improver B2, 1 g of KBM-403 was added to the varnish as an adhesion improver. As for the adhesiveness with the substrate, all peeling was observed. In the evaluation of the photosensitivity, the sensitivity decrease was 25 mJ / cm ² , but a pattern of 40 μm or more remained.

Comparative Example 10 (Synthesis of adhesion improver D1)
3.58 g (0.02 mol) of KBM-903 was dissolved in 20 g of NMP. 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 3.22 g (manufactured by Daicel Chemical Industries, Ltd., 0.01 mol) was added as a solid. The solution was stirred at 30 ° C. for 6 hours. As a result, a silane compound (D1) in which the amino group of the aminosilane compound was amide-bonded with an aromatic carboxylic acid was obtained.

The same procedure as in Example 3 was performed except that the silane compound (D1) was added to the varnish instead of the adhesion improver A2 in Example 3. As for the adhesion to the substrate, 30 pieces of 100 pieces were peeled off. In the evaluation of photosensitivity, the sensitivity reduction was 200 mJ / cm ² .

Claims (4)

It has at least 1 sort (s) of the compound represented by General formula (1)-(3), The adhesive improvement agent characterized by the above-mentioned.

(R ¹ , R ⁷ , R ¹¹ , R ¹² , R ¹³ are each an organic group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, an amino group, a carboxyl group, 2 to 10 carbon atoms. R ² , R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹⁰ , R ¹⁷ , R ¹⁸ , R ¹⁹ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁵ , R ⁶ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ²⁰ are each a group selected from an alkenyl group, a phenyl group, and a substituted phenyl group, each having 1 to 6 carbon atoms, an alkenyl group, A group selected from a phenyl group, a substituted phenyl group, and an alkoxy group having 1 to 6 carbon atoms, at least one of which is an alkoxy group having 1 to 6 carbon atoms, X is an alkyl group having 1 to 10 carbon atoms, alkylene Group, nitro group, hydroxyl group Represents a group selected from an alkoxy group, a carboxyl group, an ester group having 2 to 10 carbon atoms, and an amide group having 2 to 10 carbon atoms, XX and YY are single bonds,

Represents a group selected from R ²¹ and R ²² each represent a group selected from hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, an alkoxy group, a phenyl group, and a substituted phenyl group. p, q, s, u, v are integers of 1-4, m is an integer of 1-3, l is an integer of 0-2, a, b, k, n are integers of 0-10, d, f and g are integers from 1 to 4, t and h are integers from 1 to 100, and j is an integer from 1 to 3. The adhesion improver according to claim 1, comprising 1 to 10,000 parts by weight of a solvent with respect to 100 parts by weight of at least one of the compounds represented by the general formulas (1) to (3). Alcohols having 1 to 7 carbon atoms, esters having 2 to 20 carbon atoms, ketones having 3 to 20 carbon atoms, amides having 3 to 20 carbon atoms, and sulfur-containing solvents having 3 to 20 carbon atoms The adhesion improver according to claim 2, wherein at least one solvent selected from the above is contained in an amount of 80% or more of the total amount of the solvent. The substrate treatment liquid, wherein the adhesion improving agent according to claim 1 is a treatment liquid for treating a substrate surface.