JPH11189754A - Substrate with adhesive layer and adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive layer-attached substrate having an excellent stable adhesive strength, and to provide an adhesive film having excellent stable adhesive strengths and having different adherent properties on both the surfaces. SOLUTION: This adhesive layer-attached substrate is produced by forming an adhesive layer on a substrate having the same hydrophobic or hydrophilic tendency as that of a coupling agent. The adhesive layer comprises a thermoplastic resin layer comprising a thermoplastic resin obtained by a reaction for producing amide groups, ester groups, imide groups or ether groups and the coupling agent having a functional group capable of chemically binding to the thermoplastic resin. The adhesive layer is obtained by removing the substrate from the adhesive layer-attached substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a substrate having an adhesive layer and an adhesive film.

[0002]

2. Description of the Related Art At present, an adhesive used in the field of electronics, for example, an adhesive between a metal foil in a printed circuit board and a supporting material such as a polyimide film, and a lead frame and a semiconductor in a semiconductor device such as a resin-sealed type. For the adhesive for the element (chip) or the adhesive between the metal foil of the so-called TAB tape and the polyimide, a material excellent in high-temperature characteristics, purity, and workability is required.

Conventionally, thermosetting resins such as epoxy-based, rubber-modified epoxy-based, phenol-based, and acrylic-based adhesives which have been used as these adhesives exhibit excellent adhesive strength.
The heat resistance and purity are poor, and the adherend is contaminated by outgas which is a by-product during curing.

On the other hand, a thermoplastic resin having high heat resistance has been proposed as an adhesive which is excellent in heat resistance and hardly causes outgassing because it does not require curing (for example, Japanese Unexamined Patent Publication No. Sho 6).
1-1143479 and JP-A-1-268778). However, when these thermoplastic resins are used as adhesives of the melt-bonding type, the viscosity at the time of melt-bonding is low, so that the thickness of the adhesive decreases due to foaming at the time of bonding due to moisture absorption and excessive flow at the time of bonding. Is large. In order to solve such problems, drying the moisture absorption of the adhesive before bonding and adjusting the bonding temperature and bonding pressure showed a certain improvement effect, but these methods are easily stable. It is difficult to obtain a good adhesive strength,
There was a need for further improvements.

As one means for solving the above problems, it has been proposed to add a coupling agent having a functional group capable of chemically bonding to the thermoplastic resin in the synthesis step into the thermoplastic resin. However, when processing / forming a thermoplastic resin into a plate, film or thin film, the coupling agent concentration is affected by the environmental conditions and the physical properties of jigs and substrate materials used for processing / or forming, and the In some cases, the adhesive strength is lowered on the surface of the resin, and as a result, there is a problem that the bonding strength is not stable.

[0006]

DISCLOSURE OF THE INVENTION The inventions according to claims 1 and 2 provide a substrate with an adhesive which is excellent in adhesive strength and stable in adhesive strength. The third and fourth aspects of the present invention provide a substrate with an adhesive having different adhesive properties on both surfaces and having a stable adhesive strength. The invention according to claim 5 is to provide an adhesive film having excellent adhesive strength and stable adhesive strength, and having different adhesive properties on both surfaces and having stable adhesive strength. .

[0007]

SUMMARY OF THE INVENTION The present invention has a thermoplastic resin obtained by a reaction for producing an amide group, an ester group, an imide group or an ether group, and a functional group capable of chemically bonding to the thermoplastic resin. The present invention relates to a substrate provided with an adhesive layer, wherein an adhesive layer comprising a thermoplastic resin layer containing a coupling agent is formed on a substrate having the same tendency of hydrophobicity or hydrophilicity as the coupling agent. The present invention also provides
Adhesion consisting of a thermoplastic resin layer containing a thermoplastic resin obtained by a reaction producing an amide group, an ester group, an imide group or an ether group and a coupling agent having a functional group capable of chemically bonding to the thermoplastic resin And a contact angle A of water of the adhesive layer and a contact angle B of water of the substrate.

(Equation 3) Substrate with adhesive layer in the relationship of

The present invention also provides an amide group, an ester group,
An adhesive layer composed of a thermoplastic resin layer containing a thermoplastic resin obtained by a reaction for producing an imide group or an ether group and a coupling agent having a functional group capable of chemically bonding to the thermoplastic resin is heated to the heat. A base material that is formed on a substrate material having the same tendency as the thermoplastic resin and is hydrophobic or hydrophilic, and has a hydrophobic or hydrophilic property that is not the same as the thermoplastic resin of the adhesive formed on the other surface of the adhesive layer. The present invention relates to a laminated substrate having an adhesive layer. The present invention relates to a thermoplastic resin containing a thermoplastic resin obtained by a reaction producing an amide group, an ester group, an imide group or an ether group and a coupling agent having a functional group capable of chemically bonding to the thermoplastic resin. A substrate is laminated on both sides of an adhesive layer composed of two layers, and a water contact angle A of the adhesive layer, a water contact angle B of one substrate and a water contact angle C of the other substrate. But

(Equation 4) And a substrate having an adhesive layer having the following relationship:

The present invention also relates to an adhesive film obtained by removing a substrate from any of the above-mentioned substrates provided with an adhesive layer.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The above-mentioned amide group, ester group,
Thermoplastic resin obtained by a reaction generating an imide group or an ether group, that is, as a raw material thermoplastic resin, there are polyimide resin, polyester resin, polyether resin, polyamide imide resin, polyester imide resin, polyether imide resin, and the like. .

As the raw material thermoplastic resin, specifically,
Examples include a polyimide resin, a polyamideimide resin, a polyamide resin, a polyester resin, and a polyether resin.

The polyimide resin is preferably obtained by reacting a tetracarboxylic dianhydride with a diamine compound.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'
-Biphenyltetracarboxylic dianhydride, 2,3
3 ', 4'-biphenyltetracarboxylic dianhydride,
2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxy) Phenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride,
Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3 4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,3 2 ', 3'-benzophenonetetracarboxylic dianhydride, 2,3
3, ', 4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2 , 4,5-Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,
5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,
4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3 4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylene bis (trimellitic acid monoester acid anhydride), 2,2- Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride,
2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 2,
2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 4,4-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2- Hydroxyhexafluoroisopropyl) benzenebis (trimellitate anhydride),
1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitate anhydride), 1,2
-(Ethylene) bis (trimellitate anhydride), 1,3
-(Trimethylene) bis (trimellitate anhydride),
1,4- (tetramethylene) bis (trimellitate anhydride), 1,5- (pentamethylene) bis (trimellitate anhydride), 1,6- (hexamethylene) bis (trimellitate anhydride), 1,7- ( Heptamethylene) bis (trimellitate anhydride), 1,8- (octamethylene) bis (trimellitate anhydride), 1,9- (nonamethylene) bis (trimellitate anhydride), 1,10-
(Decamethylene) bis (trimellitate anhydride), 1,
12- (dodecamethylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene)
There is an aromatic tetracarboxylic acid of bis (trimellitate anhydride).

Further, as tetracarboxylic dianhydride,
Examples of the tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride include ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and pyrazine-2,3,5. , 6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8- Dimethyl-1,2,2
3,5,6,7-hexahydronaphthalene-1,2,2
5,6-tetracarboxylic dianhydride, cyclopentane-
1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,
2,3,4-cyclobutanetetracarboxylic dianhydride,
Bis (exo-bicyclo [2,2,1] heptane-2,
3-dicarboxylic anhydride) sulfone, bicyclo- (2,
2,2) -oct (7) -ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-
1,2-dicarboxylic anhydride, tetrahydrofuran-
2,3,4,5-tetracarboxylic dianhydride and the like.
As the tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride is preferable, and it is preferable to use 50 to 100 mol% based on the total amount of the tetracarboxylic dianhydride.

Examples of the diamine compound include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4 '
-Diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-
Diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,
3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-
Diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2- (3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane,
3-bis (3-aminophenoxy) benzene, 1,4-
Bis (4-aminophenoxy) benzene, 3,3'-
[1,4-phenylenebis (1-methylethylidene)]
Bisaniline, 3,4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-
[1,4-phenylenebis (1-methylethylidene)]
Bisaniline, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4 −
(3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] There are aromatic diamines such as sulfones.

The diamine compounds include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,3
-Bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetramethylpolysiloxane, and the like. The aromatic diamine compound is preferably used in an amount of 50 to 100 mol% based on the total amount of the diamine compound.

In the present invention, the tetracarboxylic dianhydride and the diamine compound are preferably reacted in substantially equimolar from the viewpoint of film properties.

The reaction between the tetracarboxylic dianhydride and the diamine compound is carried out in an organic solvent. Examples of the organic solvent include N-methylpyrrolidone, dimethylacetamide,
Dimethylformamide, 1,3-dimethyl-3,4,
5,6-tetrahydro-2 (1H) -pyrimidinone,
Nitrogen-containing compounds such as 1,3-dimethyl-2-imidazolidinone, sulfur compounds such as sulfolane and dimethylsulfoxide, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ
-Butyrolactone, lactones such as ε-caprolactone, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol (or diethyl, dipropyl, dibutyl) ether, tetraethylene glycol dimethyl ( Or ethers such as diethyl, dipropyl, dibutyl) ether, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl ( Or monoethyl) ether, tetraethylene glycol monomethyl (or monoethyl) ether, etc. Alcohols, phenols, cresols, phenols such as xylenol, ethyl acetate,
Esters such as butyl acetate, ethyl cellosolve acetate and butyl cellosolve acetate, hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane, and halogenated hydrocarbons such as trichloroethane, tetrachloroethane and monochlorobenzene are used.

These may be used alone or as a mixture. Considering solubility, low hygroscopicity, low-temperature curability, environmental safety, and the like, it is preferable to use lactones, ethers, ketones, and the like.

The reaction temperature is 80 ° C. or less, preferably from 0 to 5
Perform at 0 ° C. The reaction solution gradually thickens as the reaction proceeds. In this case, a polyamic acid which is a precursor of the polyimide resin is generated. This polyamic acid may be partially imidized, which is also included in the precursor of the polyimide resin.

The polyimide resin is obtained by dehydrating and ring-closing the above reaction product (polyamic acid). Dehydration ring closure is 120 ° C
It can be performed by a method of performing heat treatment at ~ 250 ° C (thermal imidization) or a method of using a dehydrating agent (chemical imidization).
In the case of a method of performing heat treatment at 120 ° C. to 250 ° C., the heat treatment is preferably performed while removing water generated in the dehydration reaction outside the system.
At this time, water may be azeotropically removed using benzene, toluene, xylene, or the like.

In the method of performing dehydration ring closure using a dehydrating agent, it is preferable to use an acid anhydride such as acetic anhydride, propionic anhydride, or benzoic anhydride, or a carbodiimide compound such as dicyclohexylcarbodiimide as the dehydrating agent. At this time, if necessary, a dehydration catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole and the like may be used. The dehydrating agent or the dehydrating catalyst is preferably used in an amount of 1 to 8 mol per 1 mol of the aromatic tetracarboxylic dianhydride.

The polyamideimide resin or its precursor according to the present invention may be prepared by using trimellitic anhydride or chloride of trimellitic anhydride instead of tetracarboxylic dianhydride in the production of the polyimide or its precursor. It can be produced by using a trivalent tricarboxylic anhydride such as a trimellitic anhydride derivative or a derivative thereof. In addition, it can also be produced using a diisocyanate compound in which a residue other than an amino group corresponds to the diamine compound instead of the diamine compound and other diamine compounds. Examples of the diisocyanate compound that can be used include those that can be obtained by reacting the aromatic diamine compound or another diamine compound with phosgene or thionyl chloride.

The polyamide resin in the present invention is obtained by reacting a dicarboxylic acid such as terephthalic acid, isophthalic acid or phthalic acid, or a derivative thereof such as dichloride or acid anhydride with the above-mentioned diamine compound or another diamine compound. Can be manufactured.

The polyester resin in the present invention includes the above-mentioned dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid, derivatives thereof such as dichloride and acid anhydride, and 1,4-dihydroxybenzene, bisphenol F and bisphenol A. And those obtained by reacting an aromatic diol compound such as 4,4'-dihydroxybiphenyl.

As the polyamideimide resin in the present invention, a polyamideimide resin obtained by reacting a tetracarboxylic dianhydride with a diamine compound containing isophthalic dihydrazide as an essential component is preferably used. As the tetracarboxylic dianhydride and the diamine compound, those described above are used. The molar ratio of isophthalic dihydrazide in the aromatic diamine compound is 1 to
Preferably, it is 100 mol%. When the content is less than 1 mol%, the dissolution resistance to the resin constituting the sealing material tends to decrease. When the content of isophthalic dihydrazide is large, the moisture resistance of the adhesive layer tends to decrease.
Is more preferably used, and 20 to 70 mol% is particularly preferably used. This polyamideimide resin is a compounding ratio of tetracarboxylic dianhydride and diamine compound, used organic solvent,
The synthesis method can be obtained in the same manner as in the synthesis of the polyimide resin.

As the raw material thermoplastic resin, aromatic polyimide resin, aromatic polyester resin, aromatic polyether resin, aromatic polyamideimide resin, aromatic polyesterimide resin, aromatic polyetherimide resin and the like are preferable. All of these resins are produced by polycondensing an aromatic diamine and / or a bisphenol compound as a base component with a reactive derivative such as dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid or chloride thereof as an acid component. be able to. As the acid component, an aromatic compound is preferable. The functional group which reacts with the coupling agent in these starting thermoplastic resins includes an amino group, a hydroxyl group, a carboxyl group and the like at a molecular chain terminal. Therefore, as long as the resin has these functional groups, the structure of the raw material thermoplastic resin in the present invention is not particularly limited.

Examples of the starting thermoplastic resin in the present invention include a resin having a repeating unit as shown in the following chemical formula 1.

[0029]

Embedded image

Examples of the raw material thermoplastic resin include:
There is a resin having a repeating unit represented by the following chemical formula 2 [general formula (I)].

Embedded image [However, in the general formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group or a halogen, X represents a bond,

Embedded image Wherein R ⁵ and R ⁶ each independently represent hydrogen, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group, and X is different for each repeating unit. And Y is

Embedded image (Where Ar represents an aromatic divalent group and Ar ′ represents a trivalent group), and Y may be different for each repeating unit.

Examples of the repeating unit represented by the general formula (I) include the following formulas (5) and (6).

Embedded image

Embedded image

The polymer having a repeating unit represented by the general formula (I) may be, for example, an aromatic dicarboxylic acid, an aromatic tricarboxylic acid, or a reactive derivative thereof.
[General formula (II)]

Embedded image [Wherein R ¹ , R ² , R ³ , R ⁴ , and X in the general formula (II) have the same meanings as in the general formula (I)]. can do.

In the above-mentioned aromatic dicarboxylic acid, aromatic tricarboxylic acid and aromatic tetracarboxylic acid, the aromatic ring may be a heterocyclic ring condensed, or two or more aromatic rings may be a methylene group, 2,2 or more. It may be bonded through an alkylene group such as a 2-isopropylidene group, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, a sulfide group, or the like. Further, a substituent that does not participate in the condensation reaction, such as an alkoxy group, an allyloxy group, an alkylamino group, and a halogen atom, may be introduced into the aromatic ring.

The aromatic dicarboxylic acid is one in which two carboxyl groups are bonded to an aromatic ring. Specifically, terephthalic acid, isophthalic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4 ' Examples thereof include -diphenylsulfonedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, and 1,5-naphthalenedicarboxylic acid, and terephthalic acid and isophthalic acid are preferred because they are easily available. Examples of the reactive derivative of the aromatic dicarboxylic acid include dichloride, dipromide and diester of the aromatic dicarboxylic acid. Terephthalic acid dichloride and isophthalic acid dichloride are particularly preferred.

In the present invention, the aromatic tricarboxylic acid is
The aromatic ring is one in which two of the three carboxyl groups are bonded to adjacent carbons, specifically, trimellitic acid, 3,3,4'-benzophenone tricarboxylic acid,
2,3,4'-diphenyltricarboxylic acid, 2,3,6
-Pyridine tricarboxylic acid, 3,4,4'-benzanilide tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, 2'-methoxy-3,4,4'-diphenyl ether tricarboxylic acid, 2'-chlorobenzanilide-
3,4,4'-tricarboxylic acid and the like can be mentioned. Examples of the reactive derivative of the aromatic tricarboxylic acid include acid anhydrides, halides, esters, amides, and ammonium salts of the aromatic tricarboxylic acid. Examples of these include trimellitic anhydride, trimellitic anhydride monochloride, 1,4-dicarboxy-3-
N, N-dimethylcarbamoylbenzene, 1,4-dicarbomethoxy-3-carboxybenzene, 1,4-dicarboxy-3-carbophenoxybenzene, 2,6-dicarboxy-3-carbomethoxypyridine, 1,6 -Di-5-carbamoylnaphthalene, and ammonium salts of the above aromatic tricarboxylic acid with ammonia, dimethylamine, triethylamine and the like. Of these, trimellitic acid and trimellitic anhydride monochloride are particularly preferred.

As the aromatic diamine represented by the general formula (II), 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-
Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane,
2,2-bis [3-methyl-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dimethyl-4-
(4-aminophenoxy) phenyl] butane, 2,2-
Bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] butane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4- (4-
Aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxyphenyl] cyclopentane, bis [4- (4- Aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, 4,4'carbonylbis (p-phenyleneoxy) dianiline, 4,4'-bis (4-aminophenoxy) biphenyl and the like Of these, 2,2-bis [4- (4-aminophenoxy) phenyl] propane is preferred, and a mixture of the above diamines can be used if necessary.

Further, known diamines other than the above-mentioned aromatic diamines, for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-
Diaminodiphenyl sulfone, metaphenylenediamine, piperazine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p-xylylenediamine, m-xylylenediamine, 3-methylheptamethylenediamine, 1,3-bis (3-amino Propyl) tetramethylenediamine, 1,3-bis (3-aminopropyl) tetramethyldisiloxane and the like can be used in combination. The ratio of these diamine compounds to the entire diamine compound is preferably 40 mol% or less. If this ratio exceeds 40 mol%, thermal stability or adhesiveness tends to deteriorate.

The acidic content of the aromatic dicarboxylic acid, aromatic tricarboxylic acid or reactive derivative thereof is preferably used in an amount of 80 to 120 mol%, particularly preferably 95 to 105 mol%, based on the total amount of the diamine. .
The highest molecular weight is obtained when these are used in equimolar amounts. If the amount of the acid component is too large or too small with respect to the diamine, the molecular weight tends to decrease, and the mechanical strength, heat resistance and the like tend to decrease. In such a reaction, a known method used for a reaction between an amine and an acid can be used as it is, and various conditions and the like are not particularly limited.

For the polycondensation reaction of the aromatic dicarboxylic acid, the aromatic tricarboxylic acid or the reactive derivative thereof with the diamine, a known method can be used. By using two or more kinds of aromatic diamines, or using two or more kinds of aromatic dicarboxylic acids or reactive derivatives thereof, and two or more kinds of aromatic tricarboxylic acids or reactive derivatives thereof, A polymer having different repeating units represented by ()) can be obtained. In addition, by using an aromatic tricarboxylic acid or a reactive derivative thereof in combination, a polymer having a different repeating unit represented by the general formula (I) can be obtained. The polymer preferably has a dimethylformamide content of 0.2 to 2.0 dl / g. If the reduced viscosity is too small, the heat resistance and mechanical strength tend to decrease, and if it is too large, the adhesiveness tends to decrease.

The coupling agent used in the present invention has two or more functional groups in its molecule, at least one of which reacts with the starting thermoplastic resin, and the remaining functional groups are the same as those of the thermoplastic resin. It is a group that can react with the resin or react with each other. There are no particular restrictions on the molecular structure, molecular weight, etc., as long as it has such two or more functional groups. Examples of such a coupling agent include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent. As the functional group of the raw material thermoplastic resin, an amino group at the molecular end, a hydroxy group,
Since a carboxy group and the like can be considered, examples of the self-reactive functional group in the coupling agent include a methoxy group and an ethoxy group.

Preferred as the coupling agent in the present invention is a silane coupling agent.
(2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropylpromethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropylmethyl Dimethoxysilane, vinyltriacetoxysilane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, γ
-Mercaptopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, γ-methacryloxypropylmethylenedimethoxysilane and the like.

In the present invention, the quantitative ratio of the coupling agent to be mixed with the thermoplastic resin is such that the ratio of the coupling agent to the total solid content of both is 0.1 to 20%.
It is preferred to use parts by weight. More preferably 0.5
To 10 parts by weight. If the amount of the coupling agent is too small, the effect of preventing foaming during bonding and the effect of preventing the adhesive from flowing excessively are low. If the amount of the coupling agent is too large, the adhesive strength tends to decrease.

The above mixing can be carried out by dissolving the thermoplastic resin and the coupling agent in a polar solvent such as N-methyl-2-pyrrolidone, dimethylacetamide, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane and the like. Heat. Heating may be performed only when the obtained varnish is applied to a substrate and dried. The temperature at this time is 150 ° C. or more, preferably 150 to 200 ° C., and the time is preferably 5 minutes or more. By this heating, the thermoplastic resin and the coupling agent sufficiently react to form a fusible resin having the above-mentioned resistance to the polar organic solvent (not easily dissolved).

The thickness of the thermoplastic resin layer is not particularly limited because it varies depending on the amount of the coupling agent used, but it is preferable that the thickness be as small as possible in order to improve the adhesive strength. Also, there are various methods and apparatuses for coating and / or film forming methods, and these may be appropriately selected depending on the form and size of the thermoplastic resin.

In the present invention, as the substrate, polyethylene, polypropylene, polystyrene, polyester,
Examples include polysulfone, polyethersulfone, polyetheretherketone, polyetherimide, polyimide polyarylate, polycarbonate, polyphenylene oxide, fluororesin, glass, metal, or a composite material combining two or more of the above. Further, a surface treatment or a surface additive may be applied to the above-mentioned material, and for example, a material obtained by applying a fluorine-based coating agent or the like may be used. The form and size of the substrate material are not particularly limited, but a film or plate form is preferred because it is easy to handle.

From these substrates, a substrate having the same tendency as the coupling agent in terms of hydrophobicity or hydrophilicity or a substrate not having the same tendency is selected. Further, a coupling agent having a similar tendency to hydrophobicity or hydrophilicity with respect to a specific base material or a coupling agent not having such a tendency is selected.

The relationship between the coupling agent and the substrate having the same tendency of hydrophobicity or hydrophilicity can be determined by the contact angle of water. That is, when the contact angle A of the water of the coupling agent and the contact angle B of the water of the base material are obtained.

(Equation 5) Preferably, the relationship is

(Equation 6) More preferably, the relationship of

(Equation 7) More preferably, the following relationship is satisfied.

The relationship between the coupling agent and the substrate having the same tendency of hydrophobicity or hydrophilicity can also be determined by the contact angle of water. That is, when the contact angle A of the water of the coupling agent and the contact angle C of the water of the base material are obtained.

(Equation 8) It can be said that there is a relationship.

The adhesive layer is formed by dissolving a thermoplastic resin and a coupling agent in a solvent and heating the varnish appropriately, and then applying a varnish to the substrate by a method such as a method of applying a varnish, a method of applying a varnish by a roll coater, or a method of applying a brush. After being applied by a method or the like, it can be dried to form a film. Further, a film obtained by peeling the film may be placed on a substrate or laminated using a roll. When laminating another substrate, the other substrate may be placed on the adhesive layer formed on one substrate, or may be laminated using a roll. When the adhesive layer is obtained as a film, the three materials may be simultaneously laminated by a roll.

The adhesive layer can be obtained as a fiber reinforced sheet by impregnating the varnish with a thin cloth mat of fiber having excellent heat resistance such as glass fiber, and then drying by heating. The base material with the adhesive layer in the present invention is obtained by removing the base material, for example, by peeling it off, to obtain an adhesive film, which is used as an adhesive.

[0051]

In the substrate with an adhesive layer according to the present invention,
If the coupling agent and the base material have the same tendency for hydrophobicity or hydrophobicity, the bonding strength will be high because the coupling agent will be aligned with the surface or become dense at the surface during lamination. It is better than the other side.

[0052]

EXAMPLE 1 205 g of 2,2-bis [4 (4-aminophenoxy) phenyl] propane (0.2 g) was placed in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser tube under nitrogen. 5 mol), 69.6 g (1.2 mol) of propylene oxide
And dissolved in 1200 g of N-methyl-2-pyrrolidone. The solution is cooled to -5 DEG C. and at this temperature 101.5 g (0.5 mol) of isophthalic dichloride are added at a temperature of 2 DEG C.
It was added not to exceed 0 ° C. Stirring was continued at room temperature for 3 hours. The obtained reaction solution was put into methanol to isolate the polymer. After drying, it was dissolved in dimethylformamide, poured into methanol and reduced in pressure to obtain a purified aromatic polyamide powder. The reduced viscosity (η _{SP / C} ) of this aromatic polyamide (measured at 30 ° C. in a 0.2% by weight solution of dimethylformamide, the same applies hereinafter) is 1.
It was 02 dl / g. Obtained aromatic polyamide powder 60
g and 3.0 g of γ-glycidoxypropyltrimethoxysilane (manufactured by Dow Corning Toray Silicone Co., Ltd., silane coupling agent SH-6040) were dissolved in 200 g of N-methyl-2-pyrrolidone to obtain Varnish A. .

This varnish A was formed on a polyetheretherketone film (manufactured by Mitsui Chemicals, Inc.) to a thickness of 90 μm and dried at 100 ° C. for 10 minutes to obtain a substrate with an adhesive layer. Then, peeled off the polyetheretherketone film, fixed to an iron frame, 10 minutes at 200 ℃
After drying at 300 ° C. for 10 minutes, an adhesive film having a thickness of 25 μm was obtained.

Then, the adhesive film was cut into 5 mm squares and left in a thermo-hygrostat at 40 ° C. and 65% RH for 24 hours to obtain a 0.2 mm-thick iron-nickel alloy lead frame at 0.2 mm intervals. Was placed on an inner lead having a width of 0.2 mm and heated at 350 ° C. under a pressure of 20 kg / cm ² for 3 seconds. No deformation was observed in the adhesive film after bonding. Furthermore, a 5 mm square silicon chip is placed on the adhesive film adhered to the lead frame at 350 ° C. at a temperature of 20 kg.
/ cm ² for 3 seconds. Table 1 shows the results obtained by measuring the shear bond strength of the chip with respect to the five bonded samples using a push-pull gauge.

The contact angle between the contact angle of the polyetheretherketone film with water and the contact angle of the above-mentioned silane coupling agent (γ-glycidoxypropyltrimethoxysilane, which is obtained by forming a powder into a tablet) is defined as FACE CONTACT ANGLE ME
Table 1 shows the results of the measurement using TER CA-D.

Example 2 The shear adhesive strength of the chip was the same as in Example 1 except that Kapton F (trade name of Toray DuPont) was used as the substrate instead of the polyetheretherketone film. And the contact angles were measured. Table 1 shows the results.

COMPARATIVE EXAMPLE 1 The same procedure as in Example 1 was carried out except that Iupirex S (trade name of Ube Industries, Ltd.) was used instead of the polyetheretherketone film as the base material. The contact angle was measured. Table 1 shows the results.

[0058]

[Table 1]

EXAMPLE 3 205 g (0.5 g) of 2,2-bis [4 (4-aminophenoxy) phenyl] propane was placed in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser tube under nitrogen. Mol), 69.6 g (1.2 mol) of propylene oxide
And dissolved in 1200 g of N-methyl-2-pyrrolidone. The solution is cooled to -5 DEG C. and at this temperature 101.5 g (0.5 mol) of isophthalic dichloride are added at a temperature of 2 DEG C.
It was added not to exceed 0 ° C. Stirring was continued at room temperature for 3 hours. The obtained reaction solution was put into methanol to isolate the polymer. After drying, it was dissolved in dimethylformamide, poured into methanol and reduced in pressure to obtain a purified aromatic polyamide powder. The reduced viscosity (η _{SP / C} ) of this aromatic polyamide (measured at 30 ° C. in a 0.2% by weight solution of dimethylformamide, the same applies hereinafter) is 1.
It was 02 dl / g. Obtained aromatic polyamide powder 60
g and 3.0 g of γ-glycidoxypropyltrimethoxysilane (manufactured by Dow Corning Toray Silicone Co., Ltd., silane coupling agent SH-6040) were dissolved in 200 g of N-methyl-2-pyrrolidone to obtain Varnish A. .

This varnish A was formed on a polyetheretherketone film (manufactured by Mitsui Chemicals, Inc.) to a thickness of 90 μm and dried at 100 ° C. for 10 minutes to obtain a substrate with an adhesive layer. Then, the polyetheretherketone film was peeled off as the substrate A, and an adhesive film was obtained. Then, this film was used as a base material B on a UPILEX S (trade name of Ube Industries, Ltd.) such that the surface opposite to the surface in contact with the polyetheretherketone film was in contact with the film. Heated for minutes. Thereafter, the adhesive layer was peeled off, and the obtained film was fixed on an iron frame and heated at 300 ° C. for 10 minutes to obtain an adhesive film having a thickness of 25 μm.

Next, this adhesive film was coated with a 10 mm × 5
Cut to a square of 5 mm, the surface in contact with the base material A and the surface in contact with the base material B
Thermocompression bonding was performed at a temperature of 50 ° C. and a pressure of 20 kg / cm ² for 3 seconds. After bonding, no deformation was observed in the adhesive film. The adhesive strength of the adhered film was measured according to JIS-Z-02.
Evaluation was made at a peel strength of 90 degrees according to the method of No. 37. Table 2 shows the results.

Example 4 The procedure of Example 3 was repeated except that Kapton F (trade name of Toray DuPont) was used as the base material A in place of the polyetheretherketone film. It was evaluated by. Table 2 shows the results.

[0063]

[Table 2]

[0064]

The adhesive of the substrate with an adhesive layer according to claim 1 or 2 has excellent adhesive strength and stable and excellent characteristics with little variation in adhesive strength. Claim 3 or 4
The adhesive of the base material with the adhesive layer in the above has different properties in adhesiveness on both sides, and has excellent properties with stable adhesive strength. The adhesive film according to claim 5 has excellent adhesive strength, and has stable and excellent characteristics with little variation in adhesive strength, and has different adhesiveness on both surfaces, and also has excellent characteristics with stable adhesive strength. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 179/08 C09J 179/08

Claims (5)

[Claims] 1. A thermoplastic resin comprising a thermoplastic resin obtained by a reaction for producing an amide group, an ester group, an imide group or an ether group, and a coupling agent having a functional group capable of chemically bonding to the thermoplastic resin. A substrate with an adhesive layer, wherein an adhesive layer comprising a resin layer is formed on a substrate having the same tendency as the coupling agent in hydrophobicity or hydrophilicity. 2. A thermoplastic resin comprising a thermoplastic resin obtained by a reaction producing an amide group, an ester group, an imide group or an ether group, and a coupling agent having a functional group capable of chemically bonding to the thermoplastic resin. An adhesive layer composed of a resin layer is formed on a substrate, and the contact angle A of water of the coupling agent and the contact angle B of water of the substrate are as follows: Substrate with adhesive layer in the relationship of 3. A thermoplastic resin comprising a thermoplastic resin obtained by a reaction for producing an amide group, an ester group, an imide group or an ether group, and a coupling agent having a functional group capable of chemically bonding to the thermoplastic resin. An adhesive layer composed of a resin layer is formed on a substrate material having the same tendency as the coupling agent in terms of hydrophobicity or hydrophilicity, and the other side of the adhesive layer is formed with the coupling agent in a hydrophobic or hydrophilic state. A substrate with an adhesive layer formed by laminating substrates that do not have the same tendency. 4. A thermoplastic resin comprising a thermoplastic resin obtained by a reaction for producing an amide group, an ester group, an imide group or an ether group and a coupling agent having a functional group capable of chemically bonding to the thermoplastic resin. A base material is laminated on both sides of an adhesive layer made of a resin layer, and a water contact angle A of the coupling agent, a water contact angle B of one base material, and a water contact angle of the other base material. C is Substrate with adhesive layer in the relationship of 5. An adhesive film obtained by removing a substrate from the substrate with an adhesive layer according to claim 1.