JP2002293933A - Alkoxy group-containing silane modified polyamic acid resin composition and polyimide-silica hybrid cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an alkoxy group-containing silane modified polyamide acid resin composition capable of providing a cured material having excellent mechanical strength and heat resistance, and a transparent polyimide-silica hybrid cured material having excellent heat resistance, mechanical strength and insulation properties and causing no warpage, nor crack. SOLUTION: This silane modified polyamic acid resin composition is characterized by comprising an alkoxy group-containing silane modified polyamide acid resin obtained by reacting a polyamic acid with an epoxy group-containing alkoxysilane partial condensate prepared by subjecting an epoxy compound containing one hydroxy group in one molecule and an alkoxysilane partial condensate to a dealcoholization reaction and a polar solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silane-modified polyamic acid resin composition containing an alkoxy group-containing silane-modified polyamic acid and a solvent, a semi-cured product thereof, and a polyimide-silica hybrid cured product. In particular, a silane-modified polyamic acid resin composition containing an alkoxy group-containing silane-modified polyamic acid can be used as a resin composition for electrical insulation and an electrical insulation material using techniques such as coating, impregnation, and film forming, and as a heat-resistant adhesive. And heat-resistant coating agents.

That is, an alkoxy group-containing silane-modified polyamic acid resin composition of the present invention and a polyimide-silica hybrid cured product obtained by coating, impregnating, film forming, etc. the resin composition are used for a copper-clad board for a printed circuit board. Insulating material for liquid crystal components such as liquid crystal alignment film, electric wire coating agent, as well as electronic materials such as interlayer insulating material for PCB and build-up printed circuit board, interlayer insulating film of semiconductor, resist ink such as solder resist, conductive paste, TAB tape, etc. Useful. Further, the alkoxy group-containing silane-modified polyamic acid resin composition of the present invention is also useful as a heat-resistant adhesive such as an adhesive for printed circuit boards, a metal paint, or a heat-resistant coating agent.

[0003]

2. Description of the Related Art Polyimide resins are generally obtained by subjecting an aromatic tetracarboxylic anhydride and an aromatic diamine as raw materials to a ring-closing reaction of a polyamic acid synthesized by a condensation reaction thereof. Such a polyimide resin has excellent heat resistance and electrical properties, and is flexible, so that,
As a heat-resistant material or an insulating material, it is widely used in various forms such as films and coating agents in the fields of electronic materials, liquid crystals, adhesives, and paints.

However, with recent developments in various fields such as the field of electronic materials, polyimides used in the field are required to have higher levels of mechanical strength, low thermal expansion, insulation, and high adhesion. It has become.

In order to impart more excellent mechanical strength and low thermal expansion to the polyimide-based polymer, a filler or the like is generally added as appropriate. However, these compositions have poor mechanical strength such as elastic modulus. Although it is slightly improved, it is not sufficient. On the contrary, the obtained film tends to be brittle, and the flexibility and adhesion tend to be reduced.

Further, Japanese Patent Application Laid-Open No. 62-283153,
JP-A-63-99234, JP-A-63-9923
No. 5, JP-A-63-99236 and the like propose a silica hybrid material obtained by mixing an alkoxysilane with a polyamic acid solution. However, in the coatings obtained from these materials, silica is not sufficiently dispersed in the coatings, so that the coatings are whitened or warped, and the mechanical strength such as the elastic modulus and the heat resistance are also improved. Not enough.

[0007]

SUMMARY OF THE INVENTION The present invention provides a mechanical strength,
An object of the present invention is to provide an alkoxy group-containing silane-modified polyamic acid resin composition capable of obtaining a cured product having excellent heat resistance. In addition, by using the alkoxy group-containing silane-modified polyamic acid, a transparent cured polyimide-silica hybrid material having excellent heat resistance, mechanical strength, and insulating properties, without causing warpage, cracking, and the like can be obtained.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that a part of the carboxyl groups of the polyamic acid (1) is partially condensed with an epoxy-containing alkoxysilane (2). The present inventors have found that the above-mentioned object can be achieved by using a resin composition containing an alkoxy group-containing silane-modified polyamic acid obtained by reacting with the above), and completed the present invention.

That is, the present invention provides an epoxy group-containing compound obtained by a dealcoholation reaction between a polyamic acid (1), an epoxy compound (A) having one hydroxyl group in one molecule, and an alkoxysilane partial condensate (B). A silane-modified polyamic acid resin composition containing an alkoxy group-containing silane-modified polyamic acid obtained by reacting with an alkoxysilane partial condensate (2) and a polar solvent; A polyimide-silica hybrid cured product obtained by drying and curing a substance applied or impregnated on a substrate at a temperature of 150 to 500 ° C; applying the silane-modified polyamic acid resin composition to a substrate, Polyamic acid-silica semi-cured product obtained by drying and curing at a temperature of: Polyimide-silica hybrid cured product obtained by curing a compound at a temperature of 150 to 500 ° C .; an electrical insulating resin composition containing the alkoxy group-containing silane-modified polyamic acid; obtained from the electrical insulating resin composition The present invention relates to an electric insulating material; a heat-resistant adhesive containing the alkoxy group-containing silane-modified polyamic acid; and a coating agent containing the alkoxy group-containing silane-modified polyamic acid.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamic acid (1) constituting the alkoxy-containing silane-modified polyamic acid composition of the present invention includes a carboxyl group and an amide group in each of adjacent carbon atoms in an amide-bonded molecular skeleton. For example, a polyamic acid solution obtained by reacting a tetracarboxylic acid and a diamine in a polar solvent at a temperature of usually −20 ° C. to 60 ° C. can be used. The molecular weight of the polyamic acid (1) is not particularly limited, but preferably has a number average molecular weight of about 3,000 to 50,000.

The above tetracarboxylic acids include, for example, pyromellitic anhydride, 1,23,4-benzenetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3 , 6,7-Naphthalenetetracarboxylic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2, 3,3 ',
4'-biphenyltetracarboxylic dianhydride, 3,
3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride Thing, 2,3,3 ', 4'-
Diphenyl ether tetracarboxylic dianhydride, 3,
3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,3 ′,
4,4'-tetracarboxyphenyl) tetrafluoropropane dianhydride, 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2,2-
Bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, cyclopentanetetracarboxylic anhydride, butane-1,2,3, 4-tetracarboxylic acid, 2,
3,5-tricarboxycyclopentyl acetic anhydride, etc., which may be used alone or in combination with
Used in combination of more than one species.

Further, within the range not losing the effects of the present invention, tricarboxylic acids such as trimellitic anhydride, butane-1,2,4-tricarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, oxalic acid, Aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, bimeric acid, suberic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid and their acid anhydrides, isophthalic acid, terephthalic acid, Aromatic dicarboxylic acids such as diphenylmethane-4,4'-dicarboxylic acid and their acid anhydrides can be used in combination. However, if these ratios are too large, the insulating properties and heat resistance of the obtained cured product tend to decrease. Therefore, the use amount is usually 30 mol% or less based on the tetracarboxylic acid. Is preferred.

The above diamines include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminophenylmethane,
3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,
4′-di (m-aminophenoxy) diphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 1,4
-Diaminobenzene, 2,5-diaminotoluene, isophoronediamine, 4- (2-aminophenoxy) -1,
3-diaminobenzene, 4- (4-aminophenoxy)
-1,3-diaminobenzene, 2-amino-4- (4-
Aminophenyl) thiazole, 2-amino-4-phenyl-5- (4-aminophenyl) thiazole, benzidine, 3,3 ′, 5,5′-tetramethylbenzidine, octafluorobenzidine, o-tolidine, m-tolidine , P-phenylenediamine, m-phenylenediamine, 1,2-bis (anilino) ethane, 2,2-bis (p-aminophenyl) propane, 2,2-bis (p-
Aminophenyl) hexafluoropropane, 2,6-diaminonaphthalene, diaminobenzotrifluoride,
1,4-bis (p-aminophenoxy) benzene, 4,
4'-bis (p-aminophenoxy) biphenyl, diaminoanthraquinone, 1,3-bis (anilino) hexafluoropropane, 1,4-bis (anilino) octafluoropropane, 2,2-bis [4- (p- [Aminophenoxy) phenyl] hexafluoropropane and the like, and these are used alone or in combination of two or more.

The above-mentioned tetracarboxylic acids and the above-mentioned diamines are obtained by the following formula: (mol number of tetracarboxylic acids) / (mol number of diamines) = (0.5-0.8) / (1.2-2.0) A polyimide adduct having either a carboxylic anhydride group or an amino group at the molecular terminal obtained by reacting within the range can also be used.

The polyamic acid (1) is prepared by reacting the above tetracarboxylic acids and diamines in a polar solvent in the range of (moles of tetracarboxylic acids / moles of diamines) = 0.9 to 1.1. Obtained. The type and amount of the polar solvent are not particularly limited as long as it dissolves the polyamic acid (1) to be formed, but non-protonic solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, and cresol can be used. It is preferable to produce the polar solvent with a polyimide residue of 5 to 40% in terms of polyimide. Here, the solid residue in terms of polyimide represents the weight% of the polyimide based on the solution of the polyamic acid (1) when the polyamic acid (1) is completely cured into the polyimide. When the solid residue in terms of polyimide is less than 5%, the production cost of the polyamic acid (1) solution increases. On the other hand, 40
%, The polyamic acid (1) solution has a high viscosity at room temperature, so that handling tends to be poor. The reaction temperature of the polyamic acid is not particularly limited as long as the amic acid group remains, but is preferably adjusted to −20 to 60 ° C. When the temperature is lower than −20 ° C., it is uneconomical. When the temperature is higher than 60 ° C., the ratio of the amide acid group in the polyamic acid to the imide group increases, and the reaction point with the epoxy group-containing alkoxysilane partial condensate (2) Is undesirably reduced.

The epoxy group-containing alkoxysilane partial condensate (2) used in the present invention comprises an epoxy compound (A) having one hydroxyl group in one molecule (hereinafter simply referred to as epoxy compound (A)) and an alkoxysilane. It is obtained by a dealcoholation reaction with the partial condensate (B).

The epoxy compound (A) includes 1
The number of epoxy groups is not particularly limited as long as the epoxy compound has one hydroxyl group in the molecule. As the epoxy compound (A), the smaller the molecular weight, the better the compatibility with the alkoxysilane partial condensate (3) and the higher the heat resistance and the effect of imparting adhesion. It is suitable. As a specific example, one is added to the molecular terminal obtained by reacting epichlorohydrin with water, a dihydric alcohol or a phenol having two hydroxyl groups.
Monoglycidyl ethers having two hydroxyl groups; polyglycidyl ethers having one hydroxyl group at the molecular terminal obtained by reacting epichlorohydrin with trihydric or higher polyhydric alcohols such as glycerin and pentaerythritol; epichlorohydrin Epoxy compounds having one hydroxyl group at the molecular terminal obtained by reacting phosphorus with aminomonoalcohol; alicyclic hydrocarbon monoepoxides having one hydroxyl group in the molecule (eg, epoxidized tetrahydrobenzyl alcohol); it can. Among these epoxy compounds, glycidol is the most excellent in terms of the effect of imparting heat resistance, and has high reactivity with the alkoxysilane partial condensate (B), so that it is optimal.

As the alkoxysilane partial condensate (B)
Is represented by the general formula (1): R¹ _mSi (OR^Two)_(4-m)  (Wherein, m represents an integer of 0 or 1;¹Has 8 or more carbon atoms
A lower alkyl or aryl group, R^TwoIs carbon number 4 or less
Represents a lower alkyl group. )
Coxysilane monomer is converted to acid or base catalyst, and water
Is obtained by hydrolysis and partial condensation in the presence of
Is used.

Specific examples of the hydrolyzable alkoxysilane monomer which is a constituent material of the alkoxysilane partial condensate (B) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetraisopropoxysilane. , Methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, And trialkoxysilanes such as isopropyltriethoxysilane. In general, among these, in particular, because of high reactivity with glycidol, the alkoxysilane partial condensate (B) is preferably synthesized using 70% by mole or more of tetramethoxysilane or methyltrimethoxysilane.

As the alkoxysilane partial condensate (B), those described above can be used without particular limitation. When two or more of these examples are used in combination, the alkoxysilane partial condensate may be used. It is preferable to use 70% by weight or more of a partial condensate of tetramethoxysilane or a partial condensate of methyltrimethoxysilane in the total amount of the product (B).

The alkoxysilane partial condensate (B) has a number-average molecular weight of about 230 to 2,000.
Is preferably about 2 to 11. Si
Is less than 2, the amount of alkoxysilanes flowing out of the system together with the alcohol without reacting during the demethanol reaction with the epoxy compound (A) increases. The reactivity of the epoxy group-containing alkoxysilane partial condensate (2) with the polyamic acid (1) decreases, making it difficult to obtain the desired alkoxy group-containing silane-modified polyamic acid.

The epoxy group-containing alkoxysilane partial condensate (2) can be obtained by subjecting the epoxy compound (A) and the alkoxysilane partial condensate (B) to a dealcoholization reaction. The use ratio of the epoxy compound (A) and the alkoxysilane partial condensate (B) is not particularly limited as long as the alkoxy group substantially remains, but the obtained epoxy group-containing alkoxysilane partial condensate ( The ratio of the epoxy group in 2) is usually the equivalent of the hydroxyl group of the epoxy compound (A) / the equivalent of the alkoxyl group of the alkoxysilane condensate (B) = 0.01 / 1 to 0.5.
It is preferable that the alkoxysilane condensate (B) and the epoxy compound (A) are subjected to a dealcoholization reaction at a charge ratio of / 1. Since the proportion of the alkoxysilane partial condensate (B) that is not epoxy-modified increases when the charge ratio decreases, the polyimide-silica hybrid cured product tends to be opaque. Therefore, the charge ratio is 0.03 or more. / 1 is more preferable. In addition, when the charging ratio is increased, the epoxy group of the epoxy group-containing alkoxysilane partial condensate (2) becomes polyfunctional, and the epoxy group is easily gelled during the synthesis of the alkoxy group-containing silane-modified polyamic acid. More preferably, the ratio is 4 or less / 1.

In the reaction between the alkoxysilane partial condensate (B) and the epoxy compound (A), for example, the above-mentioned components are charged, and a dealcoholization reaction is carried out while distilling off alcohol produced by heating. The reaction temperature is about 50 to 150 ° C, preferably 70 to 110 ° C, and the total reaction time is 1
It is about 15 hours. In addition, the dealcoholation reaction was performed 11
When the reaction is carried out at a temperature exceeding 0 ° C., the molecular weight of the reaction product becomes too high with the condensation of alkoxysilane in the reaction system,
There is a tendency to increase viscosity and gel. In such a case, viscosity increase and gelation can be prevented by, for example, stopping the dealcoholation reaction during the reaction.

In the above dealcoholation reaction between the alkoxysilane partial condensate (B) and the epoxy compound (A), the epoxy ring is opened among the conventionally known ester-hydroxyl ester exchange catalysts to promote the reaction. Those that do not ring can be used. For example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin,
Lead, antimony, arsenic, cerium, boron, cadmium,
Examples thereof include metals such as manganese, and oxides, organic acid salts, halides, and alkoxides thereof. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate and tin octylate are effective.

The above reaction can be carried out in a solvent. The solvent is not particularly limited as long as it dissolves the alkoxysilane condensate and glycidol and is inert to the epoxy group of the epoxy compound (A). As such an organic solvent, for example, N-methyl-2-
It is preferable to use a solvent such as pyrrolidone, dimethylformamide, dimethylacetamide, or xylene.

The alkoxy group-containing silane-modified polyamic acid which is the object of the present invention is the polyamic acid (1)
And the epoxy group-containing alkoxysilane partial condensate (2). Polyamic acid (1)
The use ratio of the epoxy group-containing alkoxysilane partial condensate (2) and the epoxy group-containing alkoxysilane partial condensate (2) is not particularly limited.
/ (Equivalent of carboxylic acid group of tetracarboxylic acid used for polyamic acid (1)) is preferably in the range of 0.01 to 0.4. When the above value is less than 0.01, the effect of the present invention is hardly obtained, and when it exceeds 0.4, the cured polyimide-silica hybrid becomes opaque, which is not preferable. When a polyamic acid having a number average molecular weight of 20,000 or more is used, if the value is 0.3 or more, gelation is apt to occur due to a reaction between an epoxy group and a carboxylic acid group, which is not preferable.

In the production of such an alkoxy group-containing silane-modified polyamic acid composition, for example, the above-mentioned components are charged, and the reaction is carried out by heating in a substantially anhydrous state. The main purpose of this reaction is to react the carboxylic acid group of the polyamic acid (1) with the epoxy group of the epoxy group-containing alkoxysilane partial condensate (2). During the reaction, the epoxy group-containing alkoxysilane partial condensate ( It is necessary to suppress the formation of silica by the sol-gel reaction of the alkoxysilyl moiety of 2) and the ring-closing reaction of the polyamic acid to the imide group. Therefore, the reaction temperature is about 50 to 120 ° C., preferably 60 to 120 ° C.
The reaction is preferably performed at 100 ° C. for a total reaction time of about 1 to 30 hours.

In the above dealcoholization reaction, a conventionally known catalyst used for reacting an epoxy group with a carboxylic acid for accelerating the reaction can be used. 1,8-diaza-bicyclo [5,4,0] -7-
Tertiary amines such as undecene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; Imidazoles such as 2-heptadecylimidazole and benzimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methyl Imidazole tetraphenylborate, N-methylmorpholine
And tetraphenylboron salts such as tetraphenylborate. The reaction catalyst was used in an amount of 0.1 part by weight based on 100 parts by weight of the solid residue of the polyamic acid in terms of polyimide.
Preferably, it is used in a proportion of from 01 to 5 parts by weight.

The above reaction is preferably performed in a solvent. The solvent is not particularly limited as long as it dissolves the polyamic acid (1) and the epoxy group-containing alkoxysilane partial condensate (2). Examples of such a solvent include those used during the production of polyamic acid.

The alkoxy group-containing silane thus obtained
The modified polyamic acid resin composition contains alcohol in its molecule.
An alkoxy group derived from the xysilane partial condensate (B)
Have. The content of the alkoxy group is not particularly limited.
However, this alkoxy group is not
Or sol-gel by reaction with water (moisture)
Reaction and dealcohol condensation condense the mutually bonded cured products
Since it is necessary for forming
Modified polyamic acid is usually partially contracted with alkoxysilane.
50 to 95 mol% of the alkoxy group of the compound (B), preferably
Or 60-90 mol% of unreacted
Is good. Such alkoxy group-containing silane-modified polyamid
The cured product obtained from citric acid has the general formula (2): R¹ _mSiO_{(4-m) / 2}  (Wherein, m represents an integer of 0 or 1;¹Has 8 or more carbon atoms
The following shows an alkyl group or an aryl group. )
Gelled fine silica sites (higher order network of siloxane bonds)
Eye structure). The alkoxy of the present invention
The group-containing silane-modified polyamic acid is a polyamic acid.
(1) Polysiloxane in which some of the carboxylic acid groups in the silane are modified
Amic acid as the main component, but containing the alkoxy group of the present invention.
Unreacted polyamine is contained in the silane-modified polyamic acid.
Acid (1), alkoxysilane partial condensate (B), epoxy
Xyl group-containing alkoxysilane partial condensate (2)
The solvent or catalyst used may be contained. Not yet
Reaction alkoxysilane partial condensate (B), epoxy group
The contained alkoxysilane partial condensate (2) is added during curing.
Silica cured by water decomposition and polycondensation, containing alkoxy group
Integrates with silane-modified polyamic acid.

When the alkoxy-containing silane-modified polyamic acid resin composition of the present invention is used for various applications, other components are not particularly limited as long as the composition contains the alkoxy-containing silane-modified polyamic acid resin. .

The concentration of the resin composition can be appropriately adjusted by a solvent according to the purpose of use. Any solvent can be used without particular limitation as long as it can dissolve the alkoxy group-containing silane-modified polyamic acid. When it is necessary to adjust the amount of silica in the cured product for the purpose of adjusting the mechanical strength and heat resistance of the cured product, the alkoxysilane silane-modified resin composition may be added to the alkoxysilane partial condensate (B) or polyamic acid. The acid (1) may be blended. Further, in such a resin composition, when curing the alkoxysilyl site of the alkoxy group-containing silane-modified polyamic acid, to promote hydrolysis and polycondensation, a small amount of water or the like is contained in the alkoxy group-containing silane-modified polyamic acid composition. , An organic tin, or an organic acid tin-based catalyst.

In addition, the silane-modified polyamic acid resin composition may further include a filler, a release agent, a surface treatment agent, a flame retardant, and the like, as long as the effects of the present invention are not impaired. Viscosity modifier, plasticizer, antibacterial agent, fungicide,
A leveling agent, an antifoaming agent, a coloring agent, a stabilizer, a coupling agent and the like may be added.

The semi-cured polyamic acid-silica hybrid and the cured polyimide-silica hybrid of the present invention are obtained from the silane-modified polyamic acid resin composition. That is, in order to directly obtain a polyimide-silica hybrid cured product from the silane-modified polyamic acid resin composition, the composition is coated on a substrate and then cured at about 150 to 500 ° C. When the temperature is lower than 150 ° C., the ring-closing reaction from the amic acid group to the imide group becomes incomplete. When the temperature exceeds 500 ° C., the cured polyimide-silica hybrid is thermally decomposed depending on the kind of the polyamic acid, which is not preferable. As described above, the method of directly obtaining a polyimide-silica hybrid cured product does not cause a problem in obtaining a cured product having a thickness of 50 μm or less, but often produces voids and foam when producing a thick film cured product exceeding this thickness. . In such a case, it is useful to prepare a semi-cured polyamic acid-silica hybrid from the silane-modified polyamic acid resin composition, and then cure the semi-cured polyamic acid-silica hybrid cured product. Specifically, after performing processing such as coating and impregnating the silane-modified polyamic acid resin composition on a substrate, drying the solvent at a temperature of less than 150 ° C.,
A sol-gel curing reaction of the alkoxy group-containing silane-modified polyamic acid in the silane-modified polyamic acid resin composition, the unreacted alkoxysilane partial condensate (B) and the epoxy group-containing alkoxysilane partial condensate (2),
A semi-cured polyamic acid-silica hybrid is obtained.
Further, the polyamic acid-silica hybrid semi-cured product is cured at 150 to 500 ° C. to obtain a polyimide-silica hybrid cured product.

The silane-modified polyamic acid resin composition containing an alkoxy group-containing silane-modified polyamic acid of the present invention is used as a resin composition for electrical insulation, and the cured polyimide-silica hybrid material obtained by curing the same is used as an electrical insulation material. be able to. Here, the resin composition for electrical insulation and the electrical insulating material include copper-clad boards for printed boards and interlayer insulating materials for build-up printed boards, interlayer insulating films for semiconductors, resist inks such as solder resists, conductive pastes, TAB tapes, and the like. In addition to the above electronic materials, it means liquid crystal components such as liquid crystal alignment films, wire coating agents, and the like.

When preparing a copper-clad board for a printed board from the silane-modified polyamic acid resin composition of the present invention,
The manufacturing method is not particularly limited. For example, Japanese Patent Publication No. 3-78411 and Japanese Patent Application Laid-Open No. 9-121086.
And JP-A-60-243120. Specifically, the resin composition is applied to a glass plate, the solvent is evaporated at a temperature lower than 150 ° C. to produce a semi-cured film, and the resin composition is applied again and cured. This operation is repeated several times to obtain a thickness of 25 to 1
A polyimide-silica hybrid film of 00 μm is prepared and peeled from the glass plate. A conductive layer is formed on the hybrid film by electroless plating or the like to produce a copper-clad board. Alternatively, the operation of applying the resin composition on a copper foil and curing by a method of passing through a semi-cured material is repeated several times to obtain a single-sided copper-clad board having the same thickness. Usually, a polyimide film has low adhesion to a conductor layer such as copper, and an adhesive layer is usually provided between the polyimide film and the conductor layer to form a three-layer substrate. Since the cured silica hybrid has excellent adhesion to a metal such as a conductor, it is not necessary to provide a special adhesive layer.

The method for obtaining the interlayer insulating material for a build-up substrate from the resin composition for electrical insulation of the present invention is not particularly limited, and examples thereof include the following methods. Using the copper-clad board obtained by the copper-clad board manufacturing method,
A circuit is formed by resist etching. More specifically, after applying the resin composition appropriately containing rubber, filler and the like to a wiring board on which this circuit is formed by a known method such as a spray coating method, a curtain coating method, or the like, It is cured into a polyimide-silica hybrid cured product according to the method of passing through the cured product. Thereafter, if necessary, a predetermined through-hole portion or the like is drilled, and then the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, and a metal such as copper is plated. As the plating method, electroless plating and electrolytic plating are preferable, and at least one selected from oxidizing agents, alkalis, and organic solvents is used as the roughening agent. Such an operation is sequentially repeated as desired, and the interlayer insulating layer and the conductor layer having a predetermined circuit pattern can be alternately built up and formed. However, drilling of the through-hole portion is performed after forming the outermost resin insulating layer.

When an interlayer insulating film of a semiconductor is produced from the silane-modified polyamic acid resin composition of the present invention, it can be obtained by a method of directly spin-coating the resin composition on a semiconductor to obtain a hybrid cured product. When used as an interlayer insulating film, the cured product is required to have a particularly low coefficient of linear expansion. Therefore, in the resin composition for electrical insulation of the present invention, tetramethoxysilane partial condensation is used as the alkoxysilane partial condensate (3). It is preferable to use a substance.

When the silane-modified polyamic acid resin composition of the present invention is used as a resist ink such as a solder resist, it is applied on a printed circuit board by a screen printing method, and then a hybrid cured product is obtained through a semi-cured product. Depending on the method, the resist ink is cured. Preferably, as a resist ink composition, in addition to alkoxy group-containing silane-modified polyamic acid and epoxy resin curing agent, if necessary, a vinyl-based compound having an ethylenically unsaturated double bond such as an acrylate or a methacrylate. A monomer, various pigments such as phthalocyanine blue, fillers such as silica and alumina, and a leveling agent are added to obtain a resin composition for resist ink.

When the silane-modified polyamic acid resin composition of the present invention is used in a conductive paste, a spherical or flaky conductive powder such as silver or nickel must be mixed with the insulating material. The content of the conductive powder is preferably 50 to 80% by weight based on the conductive paste from the viewpoint of conductivity and economy. If the content is less than 50% by weight, the resistance tends to increase, and if it exceeds 80% by weight, there are disadvantages such as a decrease in adhesiveness and an increase in the price of the product. Since the conductive paste must have a small specific resistance change after being exposed to severe conditions such as high temperature and high humidity,
From the viewpoint of reducing the water absorption, a partial condensate of methyltrimethoxysilane is used as the alkoxysilane partial condensate (3), which is a component of the alkoxy group-containing silane-modified polyamic acid in the resin composition for electrical insulation of the present invention. Is particularly preferred.

When a TAB tape is prepared from the silane-modified polyamic acid resin composition of the present invention, for example, a cured polyimide-silica hybrid film obtained by curing the resin composition in the same manner as the above-mentioned copper clad board is used. 5
After preparing at 0 to 100 μm, a solution comprising an epoxy resin and an epoxy resin curing agent is further applied and dried to prepare a semi-cured state (B-stage state) having a film thickness of about 20 μm, and a polyethylene release film of 20 μm The layers are overlapped with each other, heated to about 100 ° C. and pressure-bonded to form a TAB tape.

When a liquid crystal alignment film is prepared from the silane-modified polyamic acid resin composition of the present invention, the resin composition is usually applied to a substrate as it is, and for example, a transparent electrode such as ITO (Indium Tin Oxide) is prepared in advance. A polyimide-silica hybrid layer is formed on the liquid crystal holding substrate on which is formed by a method such as a spraying method or the like by directly or through a semi-cured material, and the surface is rubbed to form a liquid crystal alignment film. It is said.

The silane-modified polyamic acid resin composition of the present invention can be used as a heat-resistant adhesive or a heat-resistant coating agent.

When the silane-modified polyamic acid resin composition of the present invention is used as an adhesive for printed circuit boards,
As described in JP-A-9-121086 and JP-A-11-8448, the resin composition is applied on a heat-resistant film such as polyimide, and the semi-cured product is applied to form an adhesive layer of a polyimide-silica hybrid cured product. After being formed, plating is performed in the same way as when the build-up interlayer insulating film is made,
Form a copper clad board.

When the silane-modified polyamic acid resin composition containing the alkoxy group-containing silane-modified polyamic acid of the present invention is used as an electric wire coating agent, for example, as described in JP-A-3-93107, Through a copper wire at a speed of about 5 to 30 cm / sec.
Heat at 0-500 ° C for about 5 minutes, and insulate about 4-10 μm
To prepare an enameled wire. To further increase the film thickness, the above operation may be repeated.

[0046]

When the silane-modified polyamic acid resin composition using the alkoxy-containing silane-modified polyamic acid of the present invention is used, a cured product excellent in heat resistance and mechanical strength and free from voids (bubbles) is obtained. Cured product can be prepared.

[0047]

The present invention will be described below in detail with reference to examples and comparative examples.

Production Example 1 (Production of Epoxy Group-Containing Alkoxysilane Partial Condensate (2)) Glycidol (manufactured by NOF CORPORATION) was equipped with a stirrer, a water separator, a thermometer and a nitrogen gas inlet tube. 1400 g of trade name “Epiol OH”) and a partial condensate of tetramethoxysilane (trade name “methyl silicate 51” manufactured by Tama Chemical Co., Ltd., average number of Si is 4) 8957.9
g, the temperature was raised to 90 ° C. while stirring under a nitrogen stream, and 2.0 g of dibutyltin dilaurate was added as a catalyst to cause a reaction. During the reaction, the produced methanol was distilled off using a water separator, and cooled when the amount reached about 630 g. The time required for cooling after heating was 5 hours. Then, about 80 g of methanol remaining in the system was removed under reduced pressure at 13 kPa for about 10 minutes. In this way,
An epoxy group-containing alkoxysilane partial condensate (2A) was obtained. The equivalent of the hydroxyl group of the epoxy compound (A) / the equivalent of the alkoxyl group of the alkoxysilane condensate (B) (equivalent ratio) at the time of preparation = 0.10, and the epoxy equivalent was 512.
g / eq.

Production Example 2 (Production of Epoxy Group-Containing Alkoxysilane Partial Condensate (2)) Glycidol 180.0 was added to the same reactor as in Production Example 1.
g and 1926.3 g of a partial condensate of tetramethoxysilane (manufactured by Tama Chemical Co., Ltd., trade name “methyl silicate 56”, average number of Si is 10), and charged under nitrogen stream.
After the temperature was raised to 90 ° C. with stirring, 0.5 g of dibutyltin dilaurate was added as a catalyst and reacted. During the reaction, the produced methanol was distilled off using a water separator, and cooled when the amount reached about 80 g. The time required for cooling after the temperature rise was 6.5 hours. Then, 13kP
a, about 5 g of methanol remaining in the system was removed under reduced pressure for about 10 minutes. Thus, an epoxy group-containing alkoxysilane partial condensate (2B) was obtained. The equivalent of the hydroxyl group of the epoxy compound (A) at the time of preparation / the equivalent of the alkoxyl group of the alkoxysilane condensate (B) (equivalent ratio) =
0.068, epoxy equivalent is 832 g / eq.

Production Example 3 (Production of Epoxy Group-Containing Alkoxysilane Partial Condensate (2)) In the same reactor as in Production Example 1, 1400 g of glycidol was added.
And 9142.1 g of a partial condensate of methyltrimethoxysilane (trade name “MTMS-B”, manufactured by Tama Chemical Co., Ltd., average number of Si is 6), and heated to 90 ° C. while stirring under a nitrogen stream. After that, 2.0 g of dibutyltin dilaurate was added as a catalyst and reacted. During the reaction, the produced methanol was distilled off using a water separator, and the amount became about 640.
g when it was cooled. The time required for cooling after the temperature rise was 6.5 hours. Then, about 10 at 13kPa
For about 30 minutes, about 32 g of methanol remaining in the system was removed under reduced pressure. Thus, an epoxy group-containing alkoxysilane partial condensate (2C) was obtained. Incidentally, the equivalent of the hydroxyl group of the epoxy compound (A) at the time of the preparation / the equivalent of the alkoxyl group of the alkoxysilane condensate (B) (equivalent ratio) = 0.06.
8. Epoxy equivalent is 832 g / eq.

Example 1 (Production of a silane-modified polyamic acid resin composition) A 2 L three-necked flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen gas introducing tube was charged with polyamic acid (I.I.
S. T-brand Pyre-ML: monomer composition pyromellitic anhydride, 4,4'-diaminodiphenyl ether, solvent: N-methylpyrrolidone Solid residue in terms of polyimide: 15%) 1400 g and N-methylpyrrolidone 500 g were added thereto. C., and 39.4 g of an epoxy group-containing alkoxysilane partial condensate (2A) and 0.23 g of 2-methylimidazole as a catalyst were added.
For 4 hours. Cool down to room temperature, cure residue 12%
A silane-modified polyamic acid resin composition was obtained. In addition,
At the time of preparation, (equivalent of epoxy group of epoxy group-containing alkoxysilane partial condensate (2)) / (equivalent of carboxylic acid group of tetracarboxylic acid used for polyamic acid (1)) = 0.07.

Example 2 (Production of silane-modified polyamic acid resin composition) In the same apparatus as in Example 1, 1400 g of Pyre-ML was added.
And 500 g of N-methylpyrrolidone, and the temperature was raised to 80 ° C., 64.0 g of an epoxy-containing alkoxysilane partial condensate (2B) and 0.23 g of 2-methylimidazole as a catalyst were added, and the reaction was carried out at 80 ° C. for 4 hours. did. After cooling to room temperature, a silane-modified polyamic acid resin composition having a cured residue of 12% was obtained. At the time of preparation, (equivalent of epoxy group of epoxy group-containing alkoxysilane partial condensate (2)) / (equivalent of carboxylic acid group of tetracarboxylic acid used for polyamic acid (1)) = 0.07. .

Example 3 (Production of silane-modified polyamic acid resin composition) In the same apparatus as in Example 1, 1400 g of Pyre-ML was added.
And 500 g of N-methylpyrrolidone, and the temperature was raised to 80 ° C .; 40.2 g of an epoxy group-containing alkoxysilane partial condensate (2C) and 0.24 g of 2-methylimidazole as a catalyst were added, and the reaction was carried out at 80 ° C. for 4 hours. did. After cooling to room temperature, an alkoxy group-containing silane-modified polyamic acid resin composition having a cured residue of 12% was obtained. In addition, at the time of preparation, (epoxy group-containing alkoxysilane partial condensate (2)
/ Equivalent of epoxy group) / (equivalent of carboxylic acid group of tetracarboxylic acid used in polyamic acid (1)) = 0.
07.

Comparative Example 1 A polyimide varnish (Pyre-ML) was used as it was.

Comparative Example 2 A resin composition was prepared by mixing 4.4 g of tetramethoxysilane partial condensate (methyl silicate 51) with 100 g of polyimide varnish (Pyre-ML).

Examples 4 to 6, Comparative Examples 3 and 4 The silane-modified polyamic acid resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were applied on a stainless steel plate and heated at 150 ° C.
And cured at 300 ° C. for 30 minutes. This operation is repeated about 10 times, and the film thickness 5
A polyimide-silica hybrid cured product of 0 μm was obtained. This cured product of the polyimide-silica hybrid was peeled from the stainless steel plate, and used for subsequent performance evaluation.

(Warping / cracking) The obtained cured polyimide-silica hybrid was visually judged. Table 1 shows the results. ：: The cured product has no crack. ×: The cured product has warpage or cracks.

(Appearance) The resulting cured polyimide-silica hybrid was visually judged. Table 1 shows the results. ：: transparent. ×: Whitened.

[0059]

[Table 1]

Although the cured polyimide-silica product of the example was transparent and did not cause warpage or cracking, the cured product shown in Comparative Example 4 was cloudy and severely warped, so that a favorable cured film could not be formed.

(Film physical properties) Examples 4 to 6, Comparative Example 3
Cut out the cured film prepared in Step 1 with a dumbbell No. 1, and use a Tensilon tester (Orientec, trade name UCT-
500), the film was stretched at a pulling speed of 50 mm / min, and the film elongation to break and the strength and elastic modulus at break were measured. Tensile tests were performed at 25 ° C. three times by the same method, and the average value is shown in Table 2.

[0062]

[Table 2]

The polyimide-silica hybrid cured product of the example is higher in elastic modulus and breaking strength than the polyimide of the comparative example, and thus is particularly suitable as a copper-clad board for a printed board and a wire coating agent.

(Scratch resistance) A pencil scratch test was carried out according to a paint general test method of JIS K-5400.
Table 3 shows the results.

[0065]

[Table 3]

The polyimide-silica hybrid cured product of the example of the present invention has a higher pencil hardness than the polyimide of the comparative example, and is particularly suitable as a metal paint, a heat-resistant coating agent, and a wire coating agent.

(Insulation) Using the cured films obtained in Examples 4 and 6 and Comparative Example 3, the dielectric constant and the dielectric loss were measured at a frequency of 1 MHz. Table 4 shows the results.

[0068]

[Table 4]

The polyimide-silica hybrid cured product of the example has a lower lead dielectric constant than the polyimide of the comparative example, and has an interlayer insulating material for a copper-clad board for a printed board or a build-up printed board, an interlayer insulating film of a semiconductor, a resist. Ideal for electrical insulating materials such as ink, conductive paste, TAB tape, etc.

(Thermal Expansion) Examples 4 and 5 and Comparative Example 3
Using the cured film obtained in the above, with a thermal stress strain measuring device (TMA120C manufactured by Seiko Denshi Kogyo), 100 to 2
The coefficient of linear expansion at 00 ° C. was measured. Table 5 shows the results.

[0071]

[Table 5]

The cured films obtained in the examples were all
It has a low coefficient of linear expansion and is useful as an electrical insulating material.

(Adhesion) The silane-modified polyamic acid resin compositions of Examples 1 to 3 and the polyamic acid resin composition of Comparative Example 1 were applied to a glass plate and a copper plate so as to have a film thickness of 10 μm, and were heated at 150 ° C. Curing was performed at 300 ° C. for 30 minutes for 30 minutes to form a polyimide-silica hybrid cured product. A Goban cellophane tape peeling test was performed by a general test method of JIS K-5400, and the evaluation was made based on the following criteria. Table 6 shows the evaluation results. 〇: 100 to 90/100 Δ: 89 to 50/100 ×: 49 to 0/100

[0074]

[Table 6]

The polyimide-silica hybrid cured product of the examples has particularly excellent adhesion to a glass plate and is most suitable for a liquid crystal alignment plate. In addition, because the adhesion to the copper plate is better than the polyimide film of the comparative example, the copper-clad board for the printed board and the interlayer insulating material for the build-up printed board,
It is suitable for electronic materials such as a semiconductor interlayer insulating film, resist ink, and conductive paste.

(Thermal Shrinkage) Using the cured films obtained in Examples 4, 5, 6 and Comparative Example 3, JISC 23
The heat shrinkage was measured according to 8. Table 7 shows the results.

[0077]

[Table 7]

The cured product of the polyimide-silica hybrid of the example has a lower heat shrinkage than the polyimide of the comparative example, and is used for a copper clad board for a printed board, an interlayer insulating material for a build-up printed board, a TAB tape, and the like. This is preferable because the warpage is small.

Example 7 (Production of silane-modified polyamic acid resin composition) A polyamic acid (manufactured by Arakawa Chemical Industries, Ltd.) was placed in a 2 L three-necked flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen gas introduction pipe. Trade name I-30: monomer composition pyromellitic anhydride, 4,4'-diaminodiphenyl ether, solvent: dimethylacetamide Solid residue in terms of polyimide: 15%) 1400 g was heated to 80 ° C, and an epoxy group-containing alkoxysilane portion was obtained. Condensate (2A) 39.4
g and 0.23 g of 2-methylimidazole as a catalyst were added and reacted at 80 ° C. for 4 hours. After cooling to room temperature, a silane-modified polyamic acid resin composition having a cured residue of 16% was obtained. At the time of preparation, (equivalent of epoxy group of epoxy group-containing alkoxysilane partial condensate (2)) / (equivalent of carboxylic acid group of tetracarboxylic acid used for polyamic acid (1)) = 0.07. .

Example 8 (Copper clad board for printed circuit board) 100 g of silane-modified polyamic acid synthesized in Example 7
Was mixed with 0.5 g of 2-methyl-4-ethylimidazole, applied to a thick rolled copper foil having a thickness of 35 μm with an applicator, dried at 120 ° C. for 10 minutes, cured at 180 ° C. for 2 hours, and copper-clad for printed circuit boards I got a board.

Example 9 (Interlayer insulating film for build-up substrate) 0.5 g of 2-methyl-4-ethylimidazole was added to the silane-modified amic acid solution of Example 7 by a screen printing method on a substrate having an IPC B pattern. Was applied, dried at 120 ° C. for 10 minutes, and cured at 180 ° C. for 2 hours to form an interlayer insulating film having a thickness of 50 μm. Peel strength with conductor pattern (JIS C6481) is 13N
/ Cm. Next, the printed wiring board having an interlayer electrical insulating coating whose surface is roughened is subjected to a conditioner treatment,
Micro-etching, pickling, catalyzing, accelerator processing are sequentially performed, electroless copper plating is performed, and a thin copper plating of 0.3 μm thickness is applied on the roughened interlayer electric insulating coating film to produce a multilayer flexible substrate. did. The peeling strength was measured according to JIS C 6481, and was 8.0 N /
cm.

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Claims (11)

[Claims] 1. A polyamic acid (1) and one compound per molecule
Alkoxy-containing silane-modified polyamic acid obtained by reacting an epoxy-containing alkoxysilane partial condensate (2) obtained by a dealcoholation reaction between an epoxy compound having two hydroxyl groups (A) and an alkoxysilane partial condensate (B) And a polar solvent, and a silane-modified polyamic acid resin composition. 2. The silane-modified polyamic acid resin composition according to claim 1, wherein the epoxy compound (A) having one hydroxyl group in one molecule is glycidol. 3. The ratio of (equivalent of epoxy group of epoxy group-containing alkoxysilane partial condensate (2)) / (equivalent of carboxylic acid group of tetracarboxylic acid used for polyamic acid (1)) is 0.01 to 0.1. 3. The silane-modified polyamic acid resin composition according to claim 1 or 2, wherein 4. The silane-modified polyamic acid resin composition according to claim 1, wherein the alkoxysilane partial condensate (B) is a tetramethoxysilane partial condensate or a methyltrimethoxysilane partial condensate. 5. A silane-modified polyamic acid resin composition according to claim 1, which is applied to a substrate,
A polyamic acid-silica semi-cured product obtained by drying and curing at a temperature of less than ° C. 6. A polyimide obtained by applying or impregnating a substrate with the silane-modified polyamic acid resin composition according to claim 1 at a temperature of 150 to 500 ° C. -A silica hybrid cured product. 7. The semi-cured product according to claim 5, wherein the cured product is 150 to 50.
A polyimide-silica hybrid cured product obtained by curing at a temperature of 0 ° C. 8. An electrical insulating resin composition comprising the alkoxy group-containing silane-modified polyamic acid according to claim 1. 9. An electrical insulating material obtained from the electrical insulating resin composition according to claim 8. 10. A heat-resistant adhesive containing the alkoxy group-containing silane-modified polyamic acid according to claim 1. 11. A heat-resistant coating agent comprising the alkoxy group-containing silane-modified polyamic acid according to claim 1.