JP2010039270A - Positive type photosensitive insulating resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive type photosensitive insulating resin composition of which the coating film is excellent in flowability when thermocompression-bonded, and capable of forming a cured film of satisfactory adhesiveness and tightness. <P>SOLUTION: This positive type photosensitive insulating resin composition contains a polymer (A) containing a structural unit (a1) expressed by formula (1), a structural unit (a2) of specified acrylate, and a structural unit (a3) having a phenolic hydroxyl group, wherein 1-50 mass% of structural unit (a1) is contained, a compound (B) having a quinone azide group, a crosslinking agent (C), and a solvent (D). R<SP>1</SP>and R<SP>2</SP>represent a phenylene group or -COO-, R<SP>3</SP>and R<SP>4</SP>represent independently a phenyl group, a 1-6C alkyl group or alkoxyl group, R<SP>5</SP>represents a 1-6C alkyl group, n is an integer of 0-3, and m is an integer of 1-10, in the formula (1). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention provides an adhesive layer for three-dimensional mounting of a semiconductor device, an adhesive layer (underfill agent) for bonding a semiconductor device to a printed wiring board, and a sealing agent for embedding a semiconductor device in a substrate. The present invention relates to a positive photosensitive insulating resin composition to be used.

Conventionally, the photosensitive resin composition is used for various uses, and a permanent film is mentioned as one of them. Note that the term “permanent film” is used as a generic term for a film formed by a photosensitive resin composition on or between parts constituting a product, which remains after the product is completed. .
Specific examples of the permanent film include solder resist, package material, underfill agent, sealant, and a film used as an adhesive layer of a component package such as a circuit element or an adhesive layer between an integrated circuit element and a circuit board. Is mentioned.
In Patent Document 1 and Patent Document 2, a negative photosensitive resin composition comprising a first substrate on which an electrode is formed and a second substrate on which an electrode is similarly formed at a position corresponding to the electrode. A method of manufacturing an electronic component bonded by a permanent film made of is disclosed.

  However, in the method disclosed in the above patent document, since the coating film made of the photosensitive resin composition has poor fluidity at the time of thermocompression bonding, the adhesive layer and the second substrate are used when this is used as the adhesive layer. There was a problem that a gap was formed between the two and sufficient adhesiveness could not be obtained.

  In order to solve such a problem, as a technique for improving the fluidity at the time of thermocompression bonding of a coating film with a photosensitive resin composition, Patent Document 3 discloses a reaction product of an alkali-soluble resin and a crosslinkable polyvinyl ether compound. A chemically amplified positive photosensitive thermosetting resin composition comprising a product, a compound that generates an acid upon irradiation with radiation, and an epoxy resin is disclosed.

However, in this positive photosensitive thermosetting resin composition, although high fluidity is surely obtained at the time of thermocompression bonding of the coating film, the adhesion of the adhesive layer to the substrate is still insufficient, and as a result, the connection portion There is a problem that the mounting reliability cannot be sufficiently secured.
JP-A-6-21149 Japanese Patent No. 2660943 JP 2005-181976 A

  The present invention has been made in consideration of the above circumstances, and its purpose is to cure a positive-type photosensitive insulating resin composition that is used as a permanent film when the coating film is subjected to thermocompression bonding. It is an object of the present invention to provide a positive-type photosensitive insulating resin composition that can form a cured film having excellent fluidity and good adhesion and adhesion.

The positive photosensitive insulating resin composition of the present invention is
Component (A): a structural unit (a1) represented by the following general formula (1), a structural unit (a2) represented by the following general formula (2), and a structural unit (a3) having a phenolic hydroxyl group And a polymer containing 1 to 50% by mass of the structural unit (a1) represented by the general formula (1);
(B) component: a compound having a quinonediazide group;
(C) component: at least one crosslinking agent selected from the group consisting of compound (c1) having an alkyl etherified amino group, epoxy compound (c2) and oxetane compound (c3);
(D) Component: It contains a solvent.

[In General Formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a phenylene group or —COO—, R ³ and R ⁴ are each independently a phenyl group, an alkyl having 1 to 6 carbon atoms. R ⁵ is an alkyl group having 1 to 6 carbon atoms. N is an integer of 0 to 3, and m is an integer of 1 to 10. ]

[In General Formula (2), R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a hydrogen atom or a hydroxyl group. Moreover, x is an integer of 0-7. ]

In the positive photosensitive insulating resin composition of the present invention, the structural unit (a3) having the phenolic hydroxyl group is selected from the group consisting of the following general formula (3-1) to the following general formula (3-3). Preferably, it is at least one structural unit.

[In General Formula (3-1) to General Formula (3-3), R ⁸ is a hydrogen atom or a methyl group, and R ⁹ is — (CH ₂ ) _j — (where j is an integer of 0 to 3). R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Moreover, p is an integer of 1-4. ]

  In the positive photosensitive insulating resin composition, 5 to 40 parts by mass of the (B) component is contained with respect to 100 parts by mass of the (A) component, and 5 to 60 parts by mass of the (C) component. It is preferable that a part is contained.

  In addition, the positive photosensitive insulating resin composition of the present invention further has (E) component: novolak resin (e1), polymer (e2) having a structural unit derived from p-hydroxystyrene, and a phenolic hydroxyl group. Even if it is set as the structure containing the at least 1 sort (s) of polymer (however, except the said (A) component) chosen from the group which consists of a polymer (e3) which has a structural unit derived from a (meth) acrylic acid ester. Good.

  In the positive photosensitive insulating resin composition, the component (B) is contained in an amount of 5 to 40 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (E), and (C) It is preferable that 5-60 mass parts component is contained.

  Furthermore, it is preferable to contain (F) component: adhesion | attachment adjuvant.

  According to the positive-type photosensitive insulating resin composition of the present invention, it contains the polymer having the structural unit (a1) represented by the general formula (1), so that the coating film is subjected to thermocompression bonding. Therefore, excellent adhesion and adhesion are exhibited in the obtained cured film.

  Hereinafter, the present invention will be specifically described.

[Positive photosensitive insulating resin composition]
The positive-type photosensitive insulating resin composition of the present invention comprises a component (A), a component (B): a compound having a quinonediazide group, a component (C): a compound having an alkyl etherified amino group (detailed below). It contains at least one crosslinking agent selected from the group consisting of c1), epoxy compound (c2) and oxetane compound (c3), and component (D): solvent.
In addition, the positive photosensitive insulating resin composition of the present invention may contain other additives such as a phenolic hydroxyl group-containing polymer (E), an adhesion assistant (F), a sensitizer, and a leveling agent, which will be described later, as necessary. You may comprise as what contains.

[(A) component: polymer]
The component (A) contained in the positive-type photosensitive insulating resin composition of the present invention is a structural unit represented by the general formula (1) (hereinafter referred to as “siloxane bond-containing structural unit”) (a1), The structural unit represented by the general formula (2) (hereinafter referred to as “(meth) acrylic ester structure-containing structural unit”) (a2), and a structural unit having a phenolic hydroxyl group (hereinafter referred to as “phenolic hydroxyl group”). Containing structural unit ") (a3) and a siloxane bond-containing structural unit (a1). Hereinafter, the component (A) is referred to as a siloxane bond-containing polymer (A).

In the general formula (1) showing the siloxane bond-containing structural unit (a1) constituting the siloxane bond-containing polymer (A), R ¹ is a hydrogen atom or a methyl group, and R ² is a phenylene group or —COO. R ³ and R ⁴ are each independently a phenyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and R ⁵ is an alkyl group having 1 to 6 carbon atoms.
Moreover, in the said General formula (1), n is an integer of 0-3, m is an integer of 1-10.

  The positive type obtained when the content of the siloxane bond-containing structural unit (a1) is 1 to 50% by mass with respect to 100% by mass in total of all the structural units constituting the siloxane bond-containing polymer (A). The coated film made of the photosensitive insulating resin composition exhibits excellent adhesion, and exhibits excellent adhesion and adhesion in the cured film obtained. On the other hand, when the content of the siloxane bond-containing structural unit (a1) is less than 1% by mass, the cured film obtained from the positive photosensitive insulating resin composition obtained has sufficient adhesion to the adherend. There is a risk of not. Further, when the content of the siloxane bond-containing structural unit (a1) exceeds 50% by mass of the total of all the structural units constituting the siloxane bond-containing polymer (A), the obtained positive type photosensitive insulating resin composition There is a possibility that the coating film by may not have sufficient fluidity.

In the above general formula (2) showing the (meth) acrylate structure-containing structural unit (a2) constituting the siloxane bond-containing polymer (A), R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is It is a hydrogen atom or a hydroxyl group.
Moreover, in the said General formula (2), x is an integer of 0-7.

  Content of this (meth) acrylic acid ester structure containing structural unit (a2) is 1-50 mass% when the sum total of all the structural units which comprise a siloxane bond containing polymer (A) is 100 mass%. It is preferable.

The phenolic hydroxyl group-containing structural unit (a3) constituting the siloxane bond-containing polymer (A) is at least one structure selected from the group consisting of the general formula (3-1) to the general formula (3-3). Preferably it is a unit.
In the general formula (3-1) to the general formula (3-3), R ⁸ is a hydrogen atom or a methyl group, and R ⁹ is — (CH ₂ ) _j — (where j is 0 to 3). And R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Moreover, in the said general formula (3-1)-the said general formula (3-2), p is an integer of 1-4.

  The content of the phenolic hydroxyl group-containing structural unit (a3) is preferably 5 to 40% by mass when the total of all the structural units constituting the siloxane bond-containing polymer (A) is 100% by mass.

  Such a siloxane bond-containing polymer (A) includes, for example, a monomer (m1) that provides a siloxane bond-containing structural unit (a1) by polymerization, and a (meth) acrylic ester structure-containing structural unit ( It can be obtained by copolymerizing the monomer (m2) that provides a2) and the monomer (m3) that provides the phenolic hydroxyl group-containing structural unit (a3) by polymerization.

[Siloxane bond-containing structural unit (a1)]
Examples of the monomer (m1) that provides such a siloxane bond-containing structural unit (a1) include allyl silanes and methacryl silanes. Specifically, for example, 3-acryloxypropyltrimethoxysilane. , 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and the like.

[(Meth) acrylic ester structure-containing structural unit (a2)]

  Moreover, as a monomer (m2) which provides (meth) acrylic ester structure containing structural unit (a2), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n- Examples include butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

[Phenolic hydroxyl group-containing structural unit (a3)]
Examples of the monomer (m3) that provides such a phenolic hydroxyl group-containing structural unit (a3) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, N- (p -Hydroxyphenyl) acrylamide, N- (p-hydroxyphenyl) methacrylamide, N- (3,5-dimethyl-4-hydroxybenzyl) acrylamide, N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide and the like Is mentioned.

In the copolymerization for obtaining the siloxane bond-containing polymer (A), other polymerizable monomers copolymerizable with the above monomers (m1) to (m3) may be copolymerized.
Examples of other polymerizable monomers that can be copolymerized include isobornyl acrylate, n-hexyl-1,6-diacrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and benzyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, and the like.

  The siloxane bond-containing polymer (A) has a polystyrene-reduced mass average molecular weight (Mw) measured by gel permeation chromatography (GPC), and the resolution of the cured film by the resulting positive photosensitive insulating resin composition. From the viewpoints of thermal shock resistance, heat resistance, etc., for example, it is preferably 200,000 or less, more preferably 2,000 to 100,000, still more preferably 5,000 to 20,000.

  In the positive photosensitive insulating resin composition of the present invention, the content ratio of the component (A) is the amount of the component (A) or the amount of the component (A) and the component (E) used as necessary. The total amount is usually preferably 40 to 95 parts by mass, more preferably 50 to 80 parts by mass with respect to 100 parts by mass of the positive photosensitive insulating resin composition (excluding the solvent (D)). Part. When the content ratio of the component (A) or the content ratio of the component (A) and the component (E) used as necessary is within the above range, a coating film obtained from the positive photosensitive insulating resin composition obtained However, it has sufficient developability with an alkaline developer.

[(B) component: a compound having a quinonediazide group]
The compound having a quinonediazide group (hereinafter also referred to as “quinonediazide compound (B)”) as the component (B) used in the positive photosensitive insulating resin composition of the present invention is a compound having one or more phenolic hydroxyl groups. And an ester compound of 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid.
Although it does not specifically limit as a compound which has one or more phenolic hydroxyl groups for forming a quinonediazide compound (B), It has a structure represented by the following general formula (B-1)-general formula (B-5). Compounds are preferred.

[In General Formula (B-1), X ^{1 to} X ¹⁰ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Or a hydroxyl group is shown, and at least one of X ^{1 to} X ⁵ is a hydroxyl group. A is a single bond, O, S, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , C═O, or SO ₂ . ]

[In General Formula (B-2), X ^{11 to} X ²⁴ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Or a hydroxyl group is shown, and at least one of X ^{11 to} X ¹⁵ is a hydroxyl group. R ^{11 to} R ¹⁴ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[In General Formula (B-3), X ^{25 to} X ³⁹ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Or, it represents a hydroxyl group, and at least one of the combinations of X ^{25 to} X ²⁹ and X ^{30 to} X ³⁴ is a hydroxyl group. R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[In General Formula (B-4), X ^{40 to} X ⁵⁸ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Or a hydroxyl group is shown, and at least one of each of the combinations of X ^{40 to} X ⁴⁴ , X ^{45 to} X ⁴⁹ and X ^{50 to} X ⁵⁴ is a hydroxyl group. R ^{16 to} R ¹⁸ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[In the general formula ^{(B-5), X 59} ~X 72 may each have being the same or different, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, at least one of each in the combination of X ⁵⁹ to X ⁶² and X ⁶³ to X ⁶⁷ is a hydroxyl group. ]

  Examples of the quinonediazide compound (B) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 4′-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis 1,2-naphthoquinonediazide-4-sulfonic acid ester compounds such as 4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane or 1,2-naphtho And quinonediazide-5-sulfonic acid ester compounds.

  In the positive photosensitive insulating resin composition of the present invention, the content ratio of the quinonediazide compound (B) is 100 parts by mass of the (A) component or the (E) component described later, It is preferable that it is 5-40 mass parts with respect to a total of 100 mass parts with E) component, More preferably, it is 10-30 mass parts. When the content ratio is less than 5 parts by mass, there is a possibility that the exposed part may not be removed reliably, and thus a developed film having a pattern shape faithful to the mask pattern may not be obtained. On the other hand, when the content ratio exceeds 40 parts by mass, there is a possibility that the obtained pattern-shaped development film is deformed by a gas generated at the time of exposure or foams at the time of thermosetting.

[(C) component: cross-linking agent]
The crosslinking agent (hereinafter also referred to as “crosslinking agent (C)”) as the component (C) contained in the positive photosensitive insulating resin composition of the present invention is used as the component (A) and as necessary. (E) At least selected from the group consisting of a compound (c1) having an alkyl etherified amino group, an epoxy compound (c2) and an oxetane compound (c3), which acts as a crosslinking component that reacts with the component (E) It contains one cross-linking agent.

[Compound (c1) having an amino group converted to an alkyl ether]
As the compound (c1) having an alkyl etherified amino group, a compound having at least two alkyl etherified amino groups in the molecule is preferable. It is represented by the formula (c1).

Formula (c1): —NHR ^e —O—R ^f
[In general formula (c1), R ^e is an alkylene group (a divalent hydrocarbon group), and R ^f is an alkyl group. ]

Examples of the compound (c1) having an alkyl etherified amino group include nitrogen compounds such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, and (poly) methylolated urea. Examples thereof include compounds in which all or part (however, at least two) of active methylol groups (CH ₂ OH groups) are alkyl etherified. Here, the alkyl group constituting the alkyl ether is a methyl group, an ethyl group, or a butyl group, and may be the same as or different from each other. In addition, methylol groups that are not alkyletherified may be self-condensed within one molecule or may be condensed between two molecules, resulting in the formation of an oligomer component. Specifically, hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril and the like can be used.

[Epoxy compound (c2)]
The epoxy compound (c2) is not particularly limited as long as an epoxy group is contained in the molecule. For example, bisphenol A type epoxy, bisphenol F type epoxy, hydrogenated bisphenol A type epoxy, hydrogenated bisphenol F type epoxy, Bisphenol S epoxy, brominated bisphenol A epoxy, biphenyl epoxy, naphthalene epoxy, fluorene epoxy, spirocyclic epoxy, bisphenolalkane epoxy, phenol novolac epoxy, orthocresol novolak epoxy, brominated cresol novolak epoxy Epoxy, trishydroxymethane type epoxy, tetraphenylolethane type epoxy, alicyclic epoxy, alcohol type epoxy and the like can be mentioned.

[Oxetane compound (c3)]
The oxetane compound (c3) is not particularly limited as long as it has an oxetane ring in the molecule and can be cured. For example, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis-{[( 3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl 3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhex) Examples include siloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxyl) propoxy] methyl} oxetane, and oxetanyl-silsesquioxane.

  These crosslinking agents (C) can be used singly or in combination of two or more.

  In the positive-type photosensitive insulating resin composition of the present invention, the content of the crosslinking agent (C) is 100 parts by mass of the component (A), or the component (A) and (E) when the component (E) is included. It is preferable that it is 5-60 mass parts with respect to a total of 100 mass parts with a component, More preferably, it is 15-40 mass parts. When the content ratio of the crosslinking agent (C) is in the above range, a cured film having excellent chemical resistance and resolution can be formed. When the content of the crosslinking agent (C) is less than 5 parts by mass, the pattern-shaped opening may be filled during thermosetting, particularly when thermosetting by thermocompression bonding. On the other hand, when the content of the crosslinking agent (C) exceeds 60 parts by mass, development failure may occur in the development process.

  In the positive photosensitive insulating resin composition of the present invention, a crosslinking aid can be used in combination as necessary. Such crosslinking aids include glycidyl ether groups, glycidyl ester groups, glycidyl amino groups, benzyloxymethyl groups, dimethylaminomethyl groups, diethylaminomethyl groups, dimethylolaminomethyl groups, diethylolaminomethyl groups, morpholinomethyl groups. And compounds having an acetoxymethyl group, a benzoyloxymethyl group, an acetyl group, a vinyl group, an isopropenyl group, and the like.

  The crosslinking aid is blended in such an amount that the positive photosensitive insulating resin composition of the present invention exhibits sufficient curability and does not impair its purpose. Specifically, it can be blended in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the crosslinking agent (C).

[(D) component: solvent]
The solvent (hereinafter also referred to as “solvent (D)”) as the component (D) used in the positive photosensitive insulating resin composition of the present invention is such as the viscosity of the resulting positive photosensitive insulating resin composition. Such a solvent (D) is added to improve handling and storage stability, and is not particularly limited. For example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. Ethylene glycol monoalkyl ether acetates; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dimethyl ether , Propylene glycol dialkyl ethers such as propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. Propylene glycol monoalkyl ether acetates; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; ethyl acetate, acetic acid n-propyl, isopropyl acetate, n-butyl acetate, vinegar Aliphatic carboxylic acid esters such as isobutyl, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Other esters such as methyl acid, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, etc. Ketones; amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactones such as γ-butyrolacun.
These solvents can be used alone or in combination of two or more.

  In the positive photosensitive insulating resin composition of the present invention, the content ratio of the solvent (D) is usually 40 to 900 mass with respect to 100 mass parts in total of the components other than the solvent (D) in the composition. Part, and more preferably 60 to 400 parts by weight.

[(E) component: polymer]
The component (E) contained in the positive photosensitive insulating resin composition of the present invention has a novolak resin (e1), a polymer (e2) having a structural unit derived from p-hydroxystyrene, and a phenolic hydroxyl group (meta ) It contains at least one polymer selected from the group consisting of polymers (e3) having a structural unit derived from an acrylate ester (excluding the component (A)). Hereinafter, this component (E) is referred to as a phenolic hydroxyl group-containing polymer (E).

[Novolac resin (e1)]
The novolac resin (e1) can be obtained by condensing phenols and aldehydes in the presence of a catalyst. Examples of phenols to be used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and p-butylphenol. 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4, 5-Trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like can be mentioned. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.
Specific examples of such novolak resin (e1) include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and the like.

[Polymer having structural unit derived from p-hydroxystyrene (e2)]
A polymer having a structural unit derived from p-hydroxystyrene (hereinafter, also referred to as “p-hydroxystyrene-derived polymer”) (e2) is the total structural unit constituting the polymer derived from p-hydroxystyrene (e2). It is preferable that 50 mass% or more of structural units derived from p-hydroxystyrene are contained therein.
The p-hydroxystyrene-derived polymer (e2) can be obtained by polymerizing p-hydroxystyrene and other polymerizable monomers to form the p-hydroxystyrene-derived polymer (e2). Examples of the polymerizable monomer other than p-hydroxystyrene include styrene and n-butyl acrylate.

[Polymer (e3) having structural unit derived from (meth) acrylic acid ester having phenolic hydroxyl group]
Examples of the polymer having a structural unit derived from a (meth) acrylic acid ester having a phenolic hydroxyl group (hereinafter also referred to as “phenolic hydroxyl group-containing (meth) acrylic acid ester-derived polymer”) (e3) include, for example, the above-mentioned What is represented by general formula (3-2) can be mentioned.

  In the positive photosensitive insulating resin composition of the present invention, the content ratio of the component (E) is preferably 0 to 900 parts by mass, more preferably 100 parts per 100 parts by mass of the component (A). It is -400 mass parts.

[(F) component: adhesion aid]
The adhesion assistant (hereinafter also referred to as “adhesion assistant (F)”), which is the component (F) used in the positive photosensitive insulating resin composition of the present invention, is a functional silane coupling agent. Preferably, for example, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group, specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, Vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 1,3,5- N-tris (trimethoxysilylpropyl) isocyanurate and the like can be mentioned.

  In the positive photosensitive insulating resin composition of the present invention, the content ratio of the adhesion assistant (F) is (A) when 100 parts by mass of the component (A) or the component (E) described later is included. It is preferable that it is 0.5-10 mass parts with respect to a total of 100 mass parts of a component and (E) component, More preferably, it is 0.5-5 mass parts. When the content ratio of the adhesion assistant (F) is in the above range, the cured film obtained by the positive photosensitive insulating resin composition has high adhesion to the adherend.

[Other additives]
The positive-type photosensitive insulating resin composition of the present invention includes, as other additives, inorganic fillers, sensitizers, leveling agents, acid generators, and the like, and the characteristics of the positive-type photosensitive insulating resin composition of the present invention are impaired. It can also be contained to the extent that it does not exist.

[Method for preparing positive-type photosensitive insulating resin composition]
The preparation method of the positive photosensitive insulating resin composition of the present invention is not particularly limited, and a normal preparation method can be applied. It can also be prepared by stirring a sample bottle with each component in it and completely plugged on the wave rotor.

[Permanent film]
The cured film made of the positive photosensitive insulating resin composition of the present invention includes a solder resist, a package material, an underfill agent, a sealant, and an adhesive layer of a component package such as a circuit element or an integrated circuit element related to a semiconductor device. It can be used as a permanent film such as a film used as an adhesive layer with a circuit board.
For example, the cured film is applied to a support (a copper foil with resin, a copper-clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, etc.), and dried to volatilize the solvent and the like. Formed, and then exposed through a desired mask pattern, developed with an alkaline developer to dissolve and remove the exposed portion, washed with water, and dried to obtain a developed film having a desired pattern shape, Then, it can obtain by heating the said developing film and thermosetting.

When a permanent film is used for bonding two substrates, a developing film is used as an adhesion film, for example, a coating film is formed on one substrate, and this is exposed to form a developing film having an appropriate pattern shape. In addition, by thermocompression bonding with the other substrate laminated so that the developed film is interposed, the developed film can be thermally cured and bonded.
In this thermocompression bonding, first, the developing film is melted and fluidity is imparted, and the developing film is thermoset by proceeding with crosslinking by the component (C) in a state of following the uneven surface of the substrate. It is considered a thing.

  As a method for applying the positive photosensitive insulating resin composition to the support, for example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method can be employed. The thickness of the coating film can be appropriately controlled by adjusting the coating method and the solid content concentration and viscosity of the positive photosensitive insulating resin composition.

Examples of the radiation used for the exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a g-line stepper, and an i-line stepper, an electron beam, and a laser beam. The exposure amount is appropriately selected depending on the light source to be used, the thickness of the coating film, and the like. For example, when the ultraviolet ray from a high-pressure mercury lamp is irradiated and the thickness of the coating film is 10 to 50 μm, 1 , 50,000 to 50,000 J / m ² .

Examples of the development method include a shower development method, a spray development method, an immersion development method, a paddle development method, and the like. The development conditions are usually 20 to 40 ° C. for about 1 to 10 minutes.
As the alkaline developer, for example, an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, and choline is dissolved in water so that the concentration becomes about 1 to 10% by mass is used. Can be mentioned. The alkaline aqueous solution may be, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant added in an appropriate amount.

  The heating condition of the developing film is not particularly limited, but is, for example, 50 to 250 ° C., preferably 50 to 200 ° C., for about 30 minutes to 10 hours, depending on the use of the cured film.

  The heating of the developing film may be performed in two or more steps in order to sufficiently progress the thermosetting of the developing film or to prevent the pattern-shaped developing film from being deformed. In the step, the developing film can be cured by heating at a temperature of 50 to 120 ° C. for about 5 minutes to 2 hours, and in the second step for about 10 minutes to 10 hours at a temperature of 80 to 200 ° C.

  A hot plate, an oven, an infrared furnace or the like can be used for heating the developing film.

  According to the positive photosensitive insulating resin composition as described above, the coating film has excellent flow during thermocompression bonding because it contains a polymer having a siloxane bond-containing structural unit (a1). In the obtained cured film, excellent adhesiveness and adhesion are exhibited.

  Although the embodiments of the present invention have been specifically described above, the embodiments of the present invention are not limited to the above examples, and various modifications can be made.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the examples and comparative examples, “parts” and “%” indicate “parts by mass” and “% by mass” unless otherwise specified. Moreover, the weight average molecular weight (Mw) was measured by the following method.

The weight average molecular weight (Mw) was measured by the GPC method under the following conditions and indicated as a polystyrene equivalent value.
Apparatus: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSK-gel Multipore HXL-M (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1 mL / min

[Polymer Synthesis Example A-1]
30 parts of p-hydroxystyrene, 60 parts of p-hydroxymethacrylate, 55.5 parts of n-butyl acrylate, 150 parts of 3-acryloxypropyltrimethoxysilane and 4.5 parts of n-hexyl-1,6-diacrylate, The polymer (A-1) was obtained by dissolving in 450 parts of ethyl lactate, polymerizing for 6 hours using 4 parts of azobisisobutyronitrile while maintaining the reaction temperature at 80 ° C. in a nitrogen atmosphere. . It was 40,000 when the mass mean molecular weight (Mw) of this polymer (A-1) was measured by the gel permeation chromatography (GPC) of standard polystyrene conversion.

[Polymer Synthesis Examples A-2 to A-4]
Polymers [A-2] to [A-4] were obtained in the same manner as in Polymer Synthesis Example A-1, except that the type and amount of each monomer were changed according to the formulation shown in Table 1. .
However, the monomers described in Table 1 are as follows.
M-1: p-hydroxystyrene M-2: p-hydroxymethacrylate M-3: n-butyl acrylate M-4: 3-acryloxypropyltrimethoxysilane M-5: isobornyl acrylate M-6: n- Hexyl-1,6-diacrylate M-7: 2-hydroxyethyl acrylate

<Examples 1-6, Comparative Example 1>
By dissolving each component of (A) to (C) and (E) according to the formulation shown in Table 2 in 260 parts of ethyl lactate (component (D)), a positive photosensitive insulating resin composition [1 ] To [6] and a positive photosensitive insulating resin composition [7] for comparison were prepared.
However, the components described in Table 2 are as follows.

・ Quinonediazide compound (B)
B-1: 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfone 2.0 molar condensate with acid / crosslinking agent (C)
C-1: Hexamethoxymethylol melamine “Nicalac MW-390” (manufactured by Sanwa Chemical Co., Ltd.)
C-2: Compound “EX-610U-P” represented by the following formula (X) (manufactured by Nagase ChemteX Corporation)
C-3: 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene “OXT-121” (manufactured by Toagosei Co., Ltd.)
C-4: Tris- (3-trimethoxysilylpropyl) isocyanurate “Y-11597” (manufactured by Momentive)

・ Solvent (D)
D-1: Ethyl lactate / phenolic hydroxyl group-containing polymer (E)
E-1: Cresol novolak resin composed of m-cresol / p-cresol = 60/40 (molar ratio), polystyrene-reduced mass average molecular weight (Mw) = 6,500

  The positive photosensitive insulating resin compositions [1] to [6] and the comparative positive photosensitive insulating resin composition [7] were evaluated by the following evaluation methods (1) to (4). The results are shown in Table 3.

(1) Viscoelasticity A positive-type photosensitive insulating resin composition was applied onto a substrate by a casting method, and heated at 110 ° C. for 3 minutes to produce a film having a thickness of 40 μm. This film was cut into 5 mm × 50 mm, and viscoelasticity measurement was performed using “EXSTAR6000 TMA / ss6100” (manufactured by SII Nanotechnology Co., Ltd.) at a temperature condition of 175 ° C.

(2) Resolution A positive photosensitive insulating resin composition is applied onto a 6-inch silicon wafer by spin coating, and heated at 110 ° C. for 3 minutes using a hot plate, so that the thickness is uniform to 10 μm. A special coating film was prepared. Then, using an aligner “MA-150” (manufactured by Suss Microtec), UV exposure from a high-pressure mercury lamp through a mask in which a large number of 12.5 μm square extraction patterns are arranged has an exposure dose of 500 mJ Irradiation was performed so as to be / cm ² . Next, after immersion development at 23 ° C. for 1 minute with an aqueous 2.38 mass% tetramethylammonium hydroxide solution, the film was washed with ultrapure water for 60 seconds and air-dried with air to obtain a pattern-shaped development film. .
This developed film was observed with a scanning electron microscope “S4200” (manufactured by Hitachi, Ltd.) at a magnification of 1500 times. When the adjacent square patterns were not in contact with each other and the openings of the patterns were not filled, “good”. As evaluated.

(3) Adhesiveness A positive photosensitive insulating resin composition was applied on a silicon wafer and heated at 110 ° C. for 3 minutes using a hot plate to prepare a uniform adhesive-coated substrate having a thickness of 5 μm. The aligner “MA-150” (manufactured by Suss Microtec) was used for exposure by irradiating UV light from a high-pressure mercury lamp so that the exposure amount of light having a wavelength of 365 nm was 500 mJ / cm ² . Next, using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, it was immersed and developed at 23 ° C for 1 minute, washed with ultrapure water for 60 seconds, and then air-dried for bonding onto a silicon wafer. A film-coated substrate on which a developing film of 1 was formed was obtained. This film-coated substrate is cut into 1 cm × 1 cm, and a 2 cm × 2 cm silicon substrate section 17 is bonded onto the film-coated substrate 13 with the developing film 15 interposed therebetween, and heated to 150 ° C. as shown in FIG. In the case where the silicon substrate piece 17 is not peeled off from the film-coated substrate 13 even when it is pressed on the hot plate 11 at a load of 5 N for 20 seconds and the both ends of the silicon substrate piece 17 are supported and lifted directly above, it is determined as “good”. evaluated.

(4) Adhesiveness After heating the adhesive substrate 18 of the film-coated substrate 13 and the silicon substrate section 17 obtained in the test for measuring the adhesiveness of (3) above at 180 ° C. for 2 hours using an inert oven, As shown in FIG. 2, shear adhesive strength at 75 ° C. was measured with a needle 19 using “Bond Tester Series 4000” (manufactured by dage).

It is a schematic diagram which shows the test method of adhesiveness. It is a schematic diagram which shows the test method of adhesiveness.

Explanation of symbols

11 Hot plate 13 Substrate with film 15 Development film 17 Silicon substrate section 18 Adhesive substrate 19 Needle

Claims (6)

Component (A): a structural unit (a1) represented by the following general formula (1), a structural unit (a2) represented by the following general formula (2), and a structural unit (a3) having a phenolic hydroxyl group And a polymer containing 1 to 50% by mass of the structural unit (a1) represented by the general formula (1);
(B) component: a compound having a quinonediazide group;
(C) component: at least one cross-linking agent selected from the group consisting of compound (c1) having an alkyl etherified amino group, epoxy compound (c2) and oxetane compound (c3);
Component (D): A positive photosensitive insulating resin composition comprising a solvent.

[In General Formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a phenylene group or —COO—, R ³ and R ⁴ are each independently a phenyl group, an alkyl having 1 to 6 carbon atoms. R ⁵ is an alkyl group having 1 to 6 carbon atoms. N is an integer of 0 to 3, and m is an integer of 1 to 10. ]

[In General Formula (2), R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a hydrogen atom or a hydroxyl group. Moreover, x is an integer of 0-7. ] The structural unit (a3) having a phenolic hydroxyl group is at least one structural unit selected from the group consisting of the following general formula (3-1) to the following general formula (3-3). Item 2. The positive photosensitive insulating resin composition according to Item 1.

[In General Formula (3-1) to General Formula (3-3), R ⁸ is a hydrogen atom or a methyl group, and R ⁹ is — (CH ₂ ) _j — (where j is an integer of 0 to 3). R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Moreover, p is an integer of 1-4. ]   The component (B) is contained in an amount of 5 to 40 parts by mass and the component (C) is contained in an amount of 5 to 60 parts by mass with respect to 100 parts by mass of the component (A). Or the positive photosensitive insulating resin composition of Claim 2.   Furthermore, component (E): a novolak resin (e1), a polymer (e2) having a structural unit derived from p-hydroxystyrene, and a polymer (e3) having a structural unit derived from a (meth) acrylic acid ester having a phenolic hydroxyl group 3. The positive photosensitive insulating resin composition according to claim 1, comprising at least one polymer selected from the group consisting of: (excluding the component (A)). object.   The component (B) is contained in an amount of 5 to 40 parts by mass and the component (C) is contained in an amount of 5 to 60 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (E). The positive-type photosensitive insulating resin composition according to claim 4.   Furthermore, (F) component: Adhesion adjuvant is contained, The positive type photosensitive insulating resin composition in any one of Claims 1-5 characterized by the above-mentioned.