WO2016132784A1

WO2016132784A1 - Method for producing insulating film, insulating film, resin composition for laser abrasion, and electronic component

Info

Publication number: WO2016132784A1
Application number: PCT/JP2016/050972
Authority: WO
Inventors: 貴史土井; 西村　功
Original assignee: Jsr株式会社
Priority date: 2015-02-20
Filing date: 2016-01-14
Publication date: 2016-08-25

Abstract

The objective of the present invention is to provide a method for producing an insulating film, which uses a laser abrasion method, and wherein a resin film has high sensitivity to laser light. A method for producing an insulating film according to the present invention comprises: a step 1 wherein a resin film of a resin composition that contains a polyarylene (A) having a repeating structural unit represented by formula (A1) and a solvent (B) is formed on a substrate; a step 2 wherein the resin film is subjected to a heat treatment; and a step 3 wherein the resin film after heating is patterned by means of a laser abrasion method. (In formula (A1), Ar represents an aromatic ring; a hydroxyl group is a substituent bonded to the aromatic ring; R¹ represents a substituent bonded to the aromatic ring, which is a halogen atom or an alkyl group having 1-10 carbon atoms, and if there are a plurality of R¹ moieties, the R¹ moieties may be the same as or different from each other; a represents an integer of 1 or more; and b represents an integer of 0 or more.)

Description

Insulating film manufacturing method, insulating film, resin composition for laser ablation, and electronic component

The present invention relates to a method for producing an insulating film using a laser ablation method, an insulating film obtained by the method, a resin composition for laser ablation, and an electronic component.

Electronic components include insulating films such as surface protective films and interlayer insulating films.
As a method for forming an insulating film pattern, a photolithography method is known (for example, see Patent Document 1). In the photolithography method, a resin film is formed on a substrate by applying a photosensitive resin composition, and an exposure process and a development process are performed on the resin film to form an insulating film pattern.

However, since a developing solution and a developing device are required for the development processing, the problem of an increase in the usage amount of the developing solution due to the recent increase in the substrate size and the increase in the production amount of the substrate, and the developing device become larger. There's a problem. In addition, there are also problems such as costs related to waste liquid treatment of the developer and the environmental impact of the waste liquid.

On the other hand, a fine processing technique using a laser ablation method is known (for example, see Patent Documents 2 and 3). In laser ablation, when a solid material is irradiated with laser light with an irradiation intensity equal to or higher than a threshold, the solid material that has absorbed the laser light is sublimated, evaporated, or decomposed, and the substances constituting the solid material become atoms, molecules, or radicals. And the like, and the phenomenon that the solid material is etched in the laser irradiation portion is utilized. In the laser ablation method, it is considered that the above-mentioned problems can be solved because the development process can be omitted.

Patent Document 2 describes a resist material for excimer laser ablation containing a polyurethane compound. Patent Document 3 describes a laser ablation composition containing a vinyl polymer and nigrosine. These documents relate to a resist material that is used to form a metal pattern on a substrate and is scheduled to be peeled off.

JP 2002-341542 A Japanese Patent Laid-Open No. 10-018059 JP 2011-046766 A

An object of the present invention is to provide a method for producing an insulating film using a laser ablation method, in which the sensitivity of the resin film to laser light is high, and the insulating film obtained by the above method, and the resin composition used in the method And an electronic component having the insulating film.

The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using a resin composition having the following configuration, and the present invention has been completed.

The present invention includes, for example, the following [1] to [9].
[1] Step 1 of forming a resin film of a resin composition containing a polyarylene (A) having a repeating structural unit represented by the formula (A1) described later and a solvent (B) on a substrate, and a resin film A method for manufacturing an insulating film, comprising: a step 2 for heat treatment; and a step 3 for forming a pattern on a resin film after heating by a laser ablation method.

[2] The method for producing an insulating film according to [1], wherein the laser irradiation amount in the step 3 is 1,000 mJ / cm ² or more per 1 μm of the film thickness of the resin film after the heat treatment in the step 2.
[3] The method for manufacturing an insulating film according to [1] or [2], wherein the laser in step 3 is an excimer laser.

[4] The method for manufacturing an insulating film according to any one of [1] to [3], wherein the heating temperature of the resin film in step 2 is 150 ° C. or higher.
[5] The method for producing an insulating film according to any one of [1] to [4], wherein in the polyarylene (A), Ar in the formula (A1) is a naphthalene ring.

[6] A resin composition for laser ablation containing polyarylene (A) having a repeating structural unit represented by the formula (A1) described later and a solvent (B).
[7] An insulating film obtained by the manufacturing method according to any one of [1] to [5].
[8] An electronic component having the insulating film according to [7].
[9] An electronic component having a substrate and a rewiring layer including metal wiring and the insulating film according to [7].

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the insulating film using the laser ablation method with the high sensitivity of the resin film with respect to a laser beam can be provided, the insulating film obtained by the said method, and the resin composition used for the said method And an electronic component having the insulating film can be provided.

FIG. 1 is a top view of a base material for electrical insulation evaluation. FIG. 2 shows measurement results of the infrared spectrum of the polymer (A1) obtained in Synthesis Example 1 and the infrared spectrum after the polymer (A1) is heated at 260 ° C. for 1 hour.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described including preferred embodiments.
[Resin composition for laser ablation]
The resin composition for laser ablation of the present invention contains a polyarylene (A) and a solvent (B) described below. The resin composition for laser ablation of the present invention is also referred to as “the composition of the present invention”.

Since the resin film formed from the composition of the present invention has high sensitivity to the laser light used in the laser ablation method, the laser workability is high. For this reason, a highly accurate pattern can be formed by the laser ablation method.

<Polyarylene (A)>
The polyarylene (A) has a repeating structural unit represented by the formula (A1). The repeating structural unit represented by the formula (A1) is also referred to as “structural unit (A1)”. The structural unit (A1) is considered to form a cyclic ketone structure such as a quinone structure by being subjected to a high-temperature heat treatment (see FIG. 2).

In the formula (A1), details of each symbol are as follows.

Ar is an aromatic ring and may be a monocyclic structure or a polycyclic structure. For example, in the case of a benzene aromatic ring, the number of benzene nuclei constituting the aromatic ring is preferably 1 to 4, more preferably 1 to 3, and further preferably 1 to 2. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring, and a naphthalene ring is particularly preferable.

A hydroxyl group is a substituent bonded to an aromatic ring. R ¹ is a substituent bonded to the aromatic ring, and is a halogen atom or an alkyl group having 1 to 10 carbon atoms. When a plurality of R ¹ are present, they may be the same as or different from each other.

The “substituent bonded to the aromatic ring” may be bonded to any of the benzene nuclei when the aromatic ring has two or more benzene nuclei. Further, when the aromatic ring has two or more benzene nuclei, (1) when a plurality of hydroxyl groups are present in the same structural unit (A1), the hydroxyl groups are bonded to the same benzene nuclei contained in the aromatic ring. Or may be bonded to different benzene nuclei; (2) when a plurality of R ¹ are present in the same structural unit (A1), R ¹ is the same benzene contained in the aromatic ring. It may be bonded to a nucleus or may be bonded to a different benzene nucleus.

Examples of the halogen atom include fluorine, chlorine, and iodine.
Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms.

a is an integer of 1 or more, and is preferably an integer of 2 to 4 since it has high sensitivity to laser light. b is an integer of 0 or more, preferably an integer of 0-2.
In the structural unit (A1), the bonds * 1 and * 2 are bonded to an aromatic ring, and when the aromatic ring has two or more benzene nuclei, the same benzene nuclei contained in the aromatic ring They may be bonded or may be bonded to different benzene nuclei. Specifically, when Ar is a naphthalene ring, the bonds * 1 and * 2 may be bonded to the same benzene nucleus contained in the naphthalene ring (for example, 1 below) or bonded to different benzene nuclei. (For example, the following 2).

As the bonding site of the bond * 1 and * 2 in the structural unit (A1), when Ar is a naphthalene ring, for example, 1,2-position, 1,3-position, 1,4-position, 1,5-position, 1 6th, 1st, 7th, 1st, 8th, 2nd, 3rd, 2,4th, 2,5th, 2,6th, 2,7th, 2,8th, 3,4th, 3rd , 5th, 3,6th, 3,7th, 3,8th, 4,5th, 4,6th, 4,7th, 4th, 8th.

In the structural unit (A1), when the aromatic ring has two or more benzene nuclei, the bonds * 1 and * 2 may be structural units bonded to different benzene nuclei contained in the aromatic ring. preferable.

The structural unit (A1) is preferably a structural unit represented by the formula (A1-1), and particularly preferably a structural unit represented by the formula (A1-1-1). In these cases, the sensitivity of the resin film to laser light tends to be high.

In formula (A1-1), the hydroxyl group is a substituent bonded to the naphthalene ring, R ¹ is a substituent bonded to the naphthalene ring, and is synonymous with the same symbol in formula (A1), R ¹ May be the same as or different from each other. a1 is an integer of 1 to 6, b1 is an integer of 0 to 4, and 1 ≦ a1 + b1 ≦ 6. a1 is preferably an integer of 2 to 4, more preferably 2. b1 is preferably an integer of 0 to 2, more preferably 0.

In formula (A1-1), the bonds * 1 and * 2 may be bonded to the same benzene nucleus included in the naphthalene ring or may be bonded to different benzene nuclei. Bonds * 1 and * 2 are preferably bonded to different benzene nuclei contained in the naphthalene ring.

The polyarylene (A) has a polyarylene structure in which the main chain is formed by connecting aromatic rings (Ar) with direct bonds. By using such a polymer, it is possible to obtain an insulating film having high sensitivity of the resin film to laser light and excellent in internal stress and heat resistance.

The content of the structural unit (A1) is usually 80% by mass or more, preferably 90% by mass or more, and more preferably 99% by mass or more in 100% by mass of the polyarylene (A). When the content is in the above range, the sensitivity of the resin film to the laser light is high, and an insulating film excellent in terms of internal stress and heat resistance tends to be obtained. The content can be measured by NMR.

The weight average molecular weight (Mw) measured by gel permeation chromatography of polyarylene (A) is usually 10,000 to 200,000, preferably 15,000 to 100,000, more preferably in terms of polystyrene. 20,000 to 60,000.

When Mw is in the above range, a pattern with high resolution and high crack resistance can be formed. Details of the method for measuring Mw are as described in the examples. Mw can be adjusted by changing the kind and amount of the one-electron oxidizing agent and reaction solvent described later.

The content of polyarylene (A) is usually 50% by mass or more, preferably 60 to 100% by mass, and more preferably 70 to 100% by mass in 100% by mass of the solid content contained in the composition of the present invention. Solid content means all the components other than the solvent (B) normally contained in the composition of this invention. When the content of the polyarylene (A) is in the above range, a composition capable of forming a pattern with high resolution tends to be obtained.

Examples of the method for synthesizing polyarylene (A) include the methods described in paragraphs [0027] to [0035] of JP-A-2008-65081. Specifically, by using an aromatic compound corresponding to the structural unit (A1) as a monomer, and using another copolymerizable monomer as necessary, a polyarylene ( A) can be obtained.

From the viewpoint of molecular weight control, a coupling reaction using a one-electron oxidant is preferable. The coupling reaction using a one-electron oxidant can be performed by dissolving an aromatic compound in a reaction solvent. The phenomenon of oxidizing the oxide by taking one electron from the oxide is called one-electron oxidation, and the component that receives one electron at this time is called one-electron oxidant.
Examples of the aromatic compound include a derivative represented by the formula (a1).

In the formula (a1), Ar ′ is an aromatic ring corresponding to Ar in the formula (A1), and R ¹ , a and b have the same meanings as in the formula (A1).

Examples of the aromatic compound include naphthalene derivatives in which Ar ′ is a naphthalene ring and a = 2 in the formula (a1), and specific examples thereof include 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, Examples include 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, and 3-methyl-2,6-dihydroxynaphthalene. Further, in the formula (a1), a benzene derivative in which Ar ′ is a benzene ring and a = 1 is mentioned, and specifically, phenol is mentioned.

An aromatic compound may be used individually by 1 type, and may use 2 or more types together.
Examples of other copolymerizable monomers include p-isopropenylphenol, ethynylstyrene, propargylic acid, 6-hexynoic acid, 2-propyn-1-ol, 1-butyn-3-ol, and 3-butyne. -3-ol, 1-pentyn-3-ol, 4-pentyn-1-ol, 3-ethynylaniline, 4-ethynylaniline, and phenylacetylene.

Other copolymerizable monomers may be used alone or in combination of two or more.
Examples of the one-electron oxidant include organometallic compounds, peracids or peroxides, diazo compounds, halogens or halogen acids, ozone, and enzymes described in JP-A-2008-65081 described above. These may be used alone or in combination of two or more.

Among the 1-electron oxidizers, organometallic compounds are preferable in terms of reaction results, and copper (II) compounds and iron (III) compounds are preferable. Specifically, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) copper (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′ , N′-Tetramethylpropylenediamine) copper (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetraethylethylenediamine) copper (II)] chloride, di-μ-hydroxo -Bis [(N, N, N ′, N′-tetraethylethylenediamine) copper (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethyl-1,6- Hexanediamine) copper (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethyl-1,8-naphthalenediamine) copper (II)] chloride, di-μ- Hydroxo-bis [(N, N, N ′, N′-tetramethylethylenedi Amine) titanium (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) cerium (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) iron] chloride is preferred.

Also, when using a combination of a plurality of one-electron oxidants [for example, a combination of an organic metal compound such as a copper (II) compound and a peracid or peroxide] and when using a one-electron oxidant alone In comparison, the oxidation rate can be greatly improved. Examples of the peracid include peracetic acid and m-chloroperbenzoic acid. Examples of the peroxide include hydrogen peroxide and t-butyl hydroperoxide.

The amount of the one-electron oxidant used is preferably 0.0001 to 10 mol, more preferably 0.01 to 5 mol, still more preferably 0.1 to 1 mol, relative to 1 mol of the aromatic compound. is there.

The reaction solvent used in the coupling reaction is preferably a monomer that forms polyarylene (A), a one-electron oxidant, and a solvent that dissolves the resulting polyarylene (A). For example, methanol, 2-methoxyethanol 2-ethoxyethanol, 3-methoxypropanol, 3-ethoxypropanol, ethyl lactate, propane lactic acid, butyl lactate, and N, N-dimethylformamide.

The reaction conditions for the coupling reaction are, for example, 10 to 100 ° C. and 0.1 to 10 hours. After completion of the coupling reaction, the reaction solution contains impurities other than polyarylene (A), such as catalyst residues. For this reason, after completion | finish of reaction, it is preferable to refine | purify by a well-known purification method, for example, the precipitation method and the liquid washing method.

<Solvent (B)>
The composition of the present invention contains a solvent (B). By using the solvent (B), the handleability of the composition can be improved, and the viscosity and storage stability can be adjusted.

As the solvent (B), for example,
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; propylene glycol monomethyl ether , Propylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether Propylene glycol dialkyl ethers and the like; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol monobutyl ether acetate;
Carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-acetate Aliphatic carboxylic acid esters such as amyl, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Other esters such as ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactones such as γ-butyrolacun Aromatic hydrocarbons such as toluene and xylene;
Is mentioned.

Among these, lactic acid esters, propylene glycol monoalkyl ether acetates, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers are preferred; ethyl lactate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether Is more preferable.

A solvent (B) may be used by 1 type and may use 2 or more types together.
In the composition of the present invention, the content of the solvent (B) is such that the solid concentration in the composition is usually 1 to 70% by mass, preferably 5 to 60% by mass, more preferably 10 to 50% by mass. It is a range.

<Crosslinking agent (C)>
The composition of the present invention may contain a crosslinking agent (C). By using the crosslinking agent (C), the insulating properties and chemical resistance of the insulating film can be improved.

Examples of the crosslinking agent (C) include a crosslinking agent (C1) having at least two groups represented by —CH ₂ OR and other crosslinking agents (C2). In the above formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acetyl group. The (C1) is also referred to as “active methylene group-containing crosslinking agent (C1)”. Among these, the crosslinking agent (C1) is preferable because an insulating film having a small internal stress can be formed.

In the composition of the present invention, when the crosslinking agent (C) is used, the content thereof is usually 5 to 50 parts by mass, preferably 10 to 40 parts by mass, more preferably 100 parts by mass of the polymer (A). Is 15 to 30 parts by mass. When the content of the crosslinking agent (C) is in the above range, a composition excellent in sensitivity and resolution is obtained, and a cured film excellent in insulation tends to be obtained.

<< Active methylene group-containing crosslinking agent (C1) >>
The active methylene group-containing crosslinking agent (C1) is a crosslinking agent having at least two groups represented by —CH ₂ OR. In the formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acetyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the crosslinking agent (C1) include a compound having two or more groups represented by the formula (C1-1) and a compound having two or more groups represented by the formula (C1-2).

In the formulas (C1-1) and (C1-2), m is 1 or 2, n is 0 or 1, m + n is 2, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or An acetyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * is a bond.

Examples of the crosslinking agent (C1) include nitrogen compounds such as polymethylolated melamine, polymethylolated glycoluril, polymethylolated guanamine, and polymethylolated urea; active methylol groups in the nitrogen compounds (CH bonded to N atom) ₂ OH group) or all of a part thereof are alkyl etherified or acetoxylated. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be the same as or different from each other. Moreover, the active methylol group which is not alkyletherified or acetoxylated may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.

Examples of the crosslinking agent (C1) include crosslinking agents described in JP-A-6-180501, JP-A-2006-178059, and JP-A-2012-226297. Specifically, melamine-based crosslinking agents such as polymethylolated melamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine; polymethylolated glycoluril, tetramethoxymethylglycoluril, tetrabutoxy Glycoluril-based crosslinking agents such as methylglycoluril; 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2,4,8,10-tetraoxospiro [ 5,5] Undecane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) propyl] 2,4,8,10-tetraoxospiro [5,5] undecane A compound obtained by methylolating guanamine, etc., and all of the active methylol groups in the compound Or guanamine-based crosslinking agent such as an alkyl etherified or acetoxylation the compounds of the part. Among these, a melamine type crosslinking agent and a guanamine type crosslinking agent are preferable.

Other examples of the crosslinking agent (C1) include a methylol group-containing phenol compound, an alkylmethylol group-containing phenol compound, and an acetoxymethyl group-containing phenol compound. Specific examples include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and compounds represented by the following formulae. It is done.

A crosslinking agent (C1) may be used by 1 type, and may use 2 or more types together.

<< Other cross-linking agent (C2) >>
Examples of the other crosslinking agent (C2) include an oxirane ring-containing compound, an oxetane ring-containing compound, an isocyanate group-containing compound (including a blocked one), an oxazoline ring-containing compound, and an aldehyde group-containing phenol compound. .

As the oxirane ring-containing compound, it is sufficient that an oxirane ring is contained in the molecule. For example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin Phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, and aliphatic epoxy resin.

Specific examples of the oxirane ring-containing compound include resorcinol diglycidyl ether, pentaerythritol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, phenyl glycidyl ether, neopentyl glycol diglycidyl ether, ethylene / polyethylene glycol diester. Examples thereof include glycidyl ether, propylene / polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether.
The other crosslinking agent (C2) may be used alone or in combination of two or more.

<Other additives>
In the composition of the present invention, other additives such as crosslinked fine particles, adhesion-imparting agents, leveling agents, antifoaming agents, surfactants, fillers and the like are used alone or in combination of two or more. Can be contained in a range that does not impair.

When the composition of the present invention contains a sensitizer and / or a crosslinking agent, the internal stress of the obtained insulating film may be increased. Therefore, when the internal stress needs to be further reduced, the present invention The composition preferably does not contain a sensitizer and / or a crosslinking agent, and more preferably contains neither a sensitizer nor a crosslinking agent.

The insulating film formed from the composition of the present invention has high processing resistance (solvent resistance) as a film. The reason is considered to be that when the resin film is heat-treated, the polyarylene (A) forms a cyclic ketone structure such as a quinone structure. For this reason, the composition of this invention has the advantage that it is not necessary to contain the crosslinking agent for improving the process tolerance of an insulating film.

Moreover, the composition of the present invention has high sensitivity to laser light used in the laser ablation method, and the resin film made of the composition has high laser processability. The reason is considered to be that when the resin film is heat-treated, the polyarylene (A) forms a cyclic ketone structure such as a quinone structure. For this reason, the composition of this invention has the advantage that it is not necessary to contain a sensitizer.

When the difference in linear expansion coefficient between the substrate on which the insulating film is formed and the insulating film (permanent film) is large, for example, by adding a filler to the composition, the linear expansion coefficient of the insulating film can be lowered. it can. If the resin film contains a filler, the sensitivity to the laser beam used in the laser ablation method may be reduced, and it may be necessary to use a large amount of a sensitizer. However, since the composition of the present invention has high sensitivity to laser light used in the laser ablation method, there is an advantage that it is not necessary to use a sensitizer.

Examples of the filler include silica, alumina, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, titanium oxide, barium sulfate, barium zirconate, calcium zirconate, barium titanate, strontium titanate, and calcium titanate. Inorganic fillers such as magnesium titanate, lead titanate, and bismuth titanate. These fillers may be used alone or in combination of two or more. The filler may be spherical, plate-shaped, or whisker (fiber) -shaped.

<Method for producing resin composition>
The composition of this invention can be manufactured by mixing each component uniformly. Moreover, in order to remove a foreign material, after mixing each component uniformly, you may filter the obtained mixture with a filter.

The composition of the present invention is useful as a composition for laser ablation. In particular, the composition of the present invention is a material for forming an insulating film such as a surface protective film, an interlayer insulating film, and a planarizing film of an electronic component by using a laser ablation method, or an insulating material for a high-density mounting substrate. It can be suitably used as a film material.

[Insulating film manufacturing method]
The method for producing an insulating film of the present invention includes a step 1 (resin film forming step) for forming a resin film of the above-described resin composition for laser ablation on a substrate, and a step 2 (heating step) for heat-treating the resin film. And a step 3 (laser ablation step) of forming a pattern on the heated resin film by a laser ablation method.

Laser ablation means that when a solid material is irradiated with laser light with an irradiation intensity equal to or higher than a threshold, the solid material that has absorbed the laser light sublimates, evaporates, or decomposes, and the substances that make up the solid material are atoms, molecules, and radicals. The solid material is emitted in various forms such as, and the solid material is etched in the laser irradiation portion. A desired pattern can be formed by irradiating a portion of the solid material to be removed while sequentially scanning with laser light.

In the manufacturing method of the present invention, since the sensitivity of the resin film to the laser beam is high, an insulating film with high resolution can be manufactured. Further, the obtained insulating film has an advantage of low internal stress. Furthermore, an insulating film having high heat resistance, chemical resistance, and insulation can be manufactured.

[1] Resin film forming step In the resin film forming step, for example, a resin film is formed by applying a resin composition for laser ablation on a substrate. For the purpose of reducing the amount of solvent contained in the resin film, for example, the drying process may be performed at a lower temperature (for example, less than 150 ° C.) than the following heating step.

Examples of the substrate include a silicon wafer, a compound semiconductor wafer, a glass substrate, a quartz substrate, a ceramic substrate, an aluminum substrate, and a substrate having a semiconductor chip on the surface of these substrates. Metal wiring such as copper wiring may be formed on the surface of these substrates.

As a method for forming a resin film of a resin composition for laser ablation on a substrate, for example, a dipping method, a spray coating method, a wire bar coating method, a blade coating method, an air knife coating method, a roll coating method, a spin coating method, The curtain coat method, the gravure printing method, the silk screen method, and the inkjet method are mentioned.

The film thickness of the resin film to be formed may be set according to its intended use, and is usually 0.1 to 100 μm, preferably 1 to 50 μm. When the thickness of the resin film is not more than the above upper limit value, it is preferable in terms of the speed of ablation and the resolution of the pattern to be formed.

[2] Heating step In the heating step, the resin film formed in the resin film forming step is heated. By heating, it is considered that the polyarylene (A) contained in the resin film forms a cyclic ketone structure such as a quinone structure, and the resin film becomes suitable for laser ablation.

The heating condition is preferably a temperature at which the polyarylene (A) contained in the resin film forms a cyclic ketone structure. The heating temperature is usually 150 ° C. or higher, preferably 180 to 350 ° C., more preferably 200 to 300 ° C. The heating time is usually 1 minute or longer, preferably 10 to 1000 minutes. For example, an oven or a hot plate is used for heating.

[3] Laser Ablation Step In the laser ablation step, a desired pattern is formed on the substrate by irradiating the heated resin film with a laser beam in a desired pattern to ablate the resin film.

The laser beam applied to the resin film after heating is not particularly limited as long as it is a laser beam that can ablate the resin film. Examples of the laser light include laser light having an oscillation wavelength of any wavelength from the ultraviolet region to the infrared region. For example, a solid laser (example: YAG laser), a liquid laser (example: dye laser), a gas laser (example) : Excimer laser). Among these, YAG laser and excimer laser are preferable. An excimer laser is particularly preferable in that the absorption by the resin film made of the resin composition for laser ablation is large and the sensitivity becomes high.

Examples of excimer lasers include F ₂ excimer laser (oscillation wavelength: 157 nm), ArF excimer laser (193 nm), KrF excimer laser (248 nm), XeCl excimer laser (308 nm), and XeF excimer laser (351 nm). Can be mentioned.

The amount of laser irradiation is preferably 1,000 mJ / cm ² or more, more preferably 2,000 to 10,000 mJ / cm ² , more preferably 1,000 mJ / cm ² or more per 1 μm of the thickness of the resin film after the heat treatment at the portion to be removed. Preferably, it is 3,000 to 8,000 mJ / cm ² .

In the present invention, a pattern can be directly drawn on a resin film by a laser ablation method. For this reason, the development process which is a wet process required in the conventional photolithography method, for example, a development process using a developer such as an alkaline aqueous solution can be omitted.

[4] Post-process If necessary, the pattern may be further subjected to heat treatment, for example, in order to sufficiently develop the characteristics as an insulating film. The heating conditions are not particularly limited, but for example, heating is performed at a temperature of 100 to 400 ° C. for about 30 minutes to 10 hours depending on the use of the insulating film. In order to prevent deformation of the pattern shape, heating can be performed in multiple stages.

Further, if necessary, a desmear process such as an oxygen plasma process may be performed in order to remove the resin film residue generated by the laser ablation.
As described above, an insulating film can be obtained. The thickness of the insulating film to be formed may be set according to its intended use, and is usually 0.1 to 100 μm, preferably 1 to 50 μm.

The internal stress of the insulating film obtained by the production method of the present invention is usually 30 MPa or less, preferably 0.1 to 25 MPa, more preferably 1 to 10 MPa. When the crosslinking agent (C) is not used, an insulating film having a lower internal stress can be formed. This internal stress can be evaluated by a stress difference between before and after the formation of the insulating film on the substrate on which the insulating film is formed.

The linear expansion coefficient of the insulating film obtained by the production method of the present invention is usually 1 to 30 ppm / K. In the present invention, for example, an insulating film having a low linear expansion coefficient comparable to that of a silicon wafer used as a substrate can be formed.

[Electronic parts]
By using the insulating film manufacturing method of the present invention, an electronic component having the above-described insulating film, for example, an electronic component having one or more insulating films selected from a surface protective film, an interlayer insulating film, and a planarizing film is manufactured. can do. Examples of the electronic component include a semiconductor device and a multilayer wiring board.

For example, an electronic component having a substrate, a metal wiring, and a rewiring layer including the insulating film can be cited. The electronic component manufacturing method includes forming the insulating film using the insulating film manufacturing method of the present invention. Process. Specifically, in this rewiring layer, a metal is filled between the patterns of the insulating film formed by the manufacturing method by plating or the like, and if necessary, an insulating film is formed and the metal is repeatedly filled. Can be formed.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following description of Examples and the like, “part” is used to mean “part by mass” unless otherwise specified.

[1] Method for measuring physical properties [1-1] Method for measuring weight average molecular weight (Mw) of polymer Mw was measured by gel permeation chromatography under the following conditions.
Column: Tosoh column TSK-M and TSK2500 connected in series Developing solvent: Tetrahydrofuran Sample concentration: 0.01% by mass
・ Temperature: 40 ℃
・ Detection method: Refractive index method ・ Standard material: Polystyrene ・ GPC apparatus: manufactured by Tosoh Corporation, apparatus name “HLC-8220-GPC”

[1-2] Polymer Identification Method The polymer was identified by H-NMR and infrared spectroscopy. Infrared spectroscopic analysis was performed by the following method. The polymer was dissolved in 2-methylethanol to prepare a solution having a solid concentration of 20% by mass. The solution was applied onto a substrate made of polyethylene terephthalate by a doctor blade method and heated at 70 ° C. for 30 minutes and 120 ° C. for 30 minutes to obtain a coating film. The coating film was peeled off from the substrate, and the coating film was fixed to a metal frame with an adhesive tape, followed by vacuum drying at 120 ° C. for 2 hours to obtain an infrared evaluation film having a thickness of 20 μm.

[2] Synthesis of Polymer [Synthesis Example 1] Synthesis of Polymer (A1) In a flask, 20.00 g (0.125 mol) of 2,6-dihydroxynaphthalene, 0.58 g (0.125 mmol) in a nitrogen atmosphere. ) Di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) copper (II)] chloride and 380 mL of 2-methoxyethanol were prepared. While stirring the mixed solution A at 25 ° C. in a nitrogen atmosphere, 13.7 g of 31 mass% hydrogen peroxide solution was dropped into the mixed solution A over 2 hours, and the mixture was stirred at 25 ° C. for 3 hours. Was prepared. Thereafter, 1000 ml of water was added to the mixed solution B. The precipitated solid was separated by filtration and the filtrate was vacuum dried at 80 ° C. to obtain a powdery polymer (A1). The weight average molecular weight of the polymer (A1) was 48,000. From H-NMR, the polymer (A1) was identified as polynaphthylene bonded to the adjacent naphthalene ring at the 1- and 5-positions of the naphthalene ring. In FIG. 2, the measurement result of the infrared spectroscopy spectrum after heating a polymer (A1) for 15 minutes at 120 degreeC and the polymer (A1) for 1 hour at 260 degreeC is shown. By the heat treatment, the peak intensity due to OH stretching near 3200 to 3500 cm ⁻¹ decreases, and a peak due to C═O stretching near 1735 cm ⁻¹ is observed. Therefore, the polymer (A1) is subjected to high temperature heat treatment. It is thought that the quinone structure was formed by receiving.

[Synthesis Example 2] Synthesis of polymer (RA1) 70 parts of pt-butoxystyrene and 10 parts of styrene were dissolved in 150 parts of propylene glycol monomethyl ether, and the reaction temperature was maintained at 70 ° C under a nitrogen atmosphere. For 10 hours using 4 parts of azobisisobutyronitrile. Thereafter, sulfuric acid was added to the reaction solution, and the reaction temperature was maintained at 90 ° C. for 10 hours, and the pt-butoxystyrene unit was deprotected and converted to the p-hydroxystyrene unit. Ethyl acetate was added to the obtained copolymer, washing with water was repeated 5 times, the ethyl acetate layer was separated, the solvent was removed, and a p-hydroxystyrene / styrene copolymer (RA1) was obtained. The weight average molecular weight of this polymer (RA1) was 9,000.

[3] Preparation of resin composition [Example 1]
100 parts of the polymer (A1) of Synthesis Example 1 and 430 parts of propylene glycol monomethyl ether as a solvent (B1) were uniformly mixed, and foreign matters were removed with a membrane filter to prepare a resin composition. Predetermined evaluation was performed using the obtained composition.

[Example 2]
100 parts of the polymer (A1) of Synthesis Example 1, 20 parts of methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd., trade name “MW-30M”) as a crosslinking agent (C1-1), solvent (B1) Was mixed uniformly in an amount of 430 parts of propylene glycol monomethyl ether, and foreign matters were removed with a membrane filter to prepare a resin composition. Predetermined evaluation was performed using the obtained composition.

[Examples 3 to 5, Comparative Example 1]
In Examples 3 to 5 and Comparative Example 1, resin compositions were prepared in the same manner as in Example 2 except that the types and amounts of the ingredients were changed as shown in Table 1. Predetermined evaluation was performed using the obtained composition.
Details of each component in Table 1 are as follows.

<< Polyarylene (A) Other Polymers >>
Polymer (A1): Polymer obtained in Synthesis Example 1 Polymer (RA1): Polymer obtained in Synthesis Example 2
<< Solvent (B) >>
B1: Propylene glycol monomethyl ether
<< Crosslinking agent (C) >>
C1-1: Methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd., trade name “MW-30M”)
C1-2: 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane methoxymethylolated compound (represented by the following formula 2) Compound)

C1-3: methoxymethylolated product of 1,1,1-tris (4-hydroxyphenyl) ethane (compound represented by the following formula 3)

C2-1: Trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name “Denacol EX321L”)

[4] The evaluation method of the evaluation resin composition is as follows.
[4-1] Laser processability A 4-inch silicon wafer is spin-coated with the resin composition obtained above, and then heated at 90 ° C. for 3 minutes using a hot plate to form a uniform resin film having a thickness of 12 μm. Was made. Subsequently, it heated at 260 degreeC for 1 hour using the convection oven. Next, using an excimer laser (manufactured by Light Machinery Co., Ltd., device name “IPEX-848”), a KrF excimer laser with a wavelength of 248 nm was irradiated to the resin film at an energy density of 500 mJ / cm ² through a pattern mask (110 shots). The irradiation amount per 1 μm thickness of the resin film is about 4580 mJ / cm ² ). Next, desmear treatment was performed by irradiating oxygen plasma at 100 W for 60 seconds with a dry etching apparatus. As described above, a pattern having a hole having a via hole diameter of about 10 μm on the surface of the resin film was formed. Thereafter, the shape of the hole in the pattern was measured using a laser microscope (manufactured by Olympus Corporation, MHL110). The ratio of the via hole diameter D on the resin film surface and the hole diameter d on the bottom surface [formula (d / D) × 100 [%]] was evaluated according to the following criteria.
○: 70% or more ×: less than 70%

[4-2] A silicon wafer having an internal stress of 8 inches is spin-coated with the resin composition obtained above, and then heated at 90 ° C. for 3 minutes using a hot plate to form a uniform resin film having a thickness of 12 μm. Produced. Subsequently, it heated at 260 degreeC for 1 hour using the convection oven, and formed the insulating film. The stress difference between the silicon wafers before and after the formation of the insulating film was measured by a stress measuring device (FLX-2320-s manufactured by TOHO Technology (formerly owned by KLA-Tencor)).

[4-3] Heat Resistance The heat resistance of the insulating film produced in the above [4-2] Internal stress column was evaluated at a 5% by mass thermal weight reduction temperature (° C.). The 5 mass% thermogravimetric decrease temperature was measured by thermogravimetric analysis (TGA) in a nitrogen atmosphere at a heating rate of 10 ° C./min.

[4-4] Electrical Insulation As shown in FIG. 1, a substrate 3 for electrical insulation evaluation having a substrate 1 and a patterned copper foil 2 formed on the substrate 1 was obtained as described above. The resin composition was applied, and then heated at 110 ° C. for 5 minutes using a hot plate to produce a substrate having a resin film having a thickness of 12 μm on the copper foil 2. Thereafter, the film was heated in a convection oven at 120 ° C. for 30 minutes, then at 150 ° C. for 30 minutes, and then at 200 ° C. for 1 hour to obtain an insulating film. The obtained test substrate was put into a migration evaluation system (AEI, EHS-221MD manufactured by Tabai Espec Co., Ltd.), and the temperature was 121 ° C., the humidity was 85%, the pressure was 1.2 atm, and the applied voltage was 5 V for 100 hours. Processed. Thereafter, the resistance value (Ω) of the test substrate was measured to confirm the electrical insulation.

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Patterned copper foil, 3 ... Base material for electrical insulation evaluation

Claims

Forming a resin film of a resin composition containing a polyarylene (A) having a repeating structural unit represented by the formula (A1) and a solvent (B) on a substrate;
Step 2 of heat-treating the resin film;
And a step 3 of forming a pattern on the heated resin film by a laser ablation method.

[In the formula (A1), Ar is an aromatic ring; a hydroxyl group is a substituent bonded to the aromatic ring; R 1 is a substituent bonded to the aromatic ring; a halogen atom or a carbon number of 1 And when there are a plurality of R 1 s , they may be the same or different from each other; a is an integer of 1 or more, and b is an integer of 0 or more. ]
The method for producing an insulating film according to claim 1, wherein the amount of laser irradiation in step 3 is 1,000 mJ / cm 2 or more per 1 μm of film thickness of the resin film after the heat treatment in step 2.
3. The method of manufacturing an insulating film according to claim 1, wherein the laser in step 3 is an excimer laser.
The method for manufacturing an insulating film according to any one of claims 1 to 3, wherein the heating temperature of the resin film in step 2 is 150 ° C or higher.
The method for producing an insulating film according to any one of claims 1 to 4, wherein in the polyarylene (A), Ar in the formula (A1) is a naphthalene ring.
A polyarylene (A) having a repeating structural unit represented by the formula (A1);
A resin composition for laser ablation containing a solvent (B).

[In the formula (A1), Ar is an aromatic ring; a hydroxyl group is a substituent bonded to the aromatic ring; R 1 is a substituent bonded to the aromatic ring; a halogen atom or a carbon number of 1 And when there are a plurality of R 1 s , they may be the same or different from each other; a is an integer of 1 or more, and b is an integer of 0 or more. ]
An insulating film obtained by the manufacturing method according to any one of claims 1 to 5.
An electronic component having the insulating film according to claim 7.
A substrate,
The electronic component which has a metal wiring and the rewiring layer containing the insulating film of Claim 7.