JP3396974B2 - Heat resistant composite film - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat resistant composite film which is useful in a wide range of fields such as flexible printed circuit boards, chip carrier tapes and packaging materials having excellent heat resistance.

[0002]

2. Description of the Related Art Conventionally, a polyester film has been mainly used as a film used for a flexible printed circuit board, a magnetic tape, etc., but its use at high temperature is extremely limited because of its low heat resistance. on the other hand,
Polyimide is known as a heat-resistant film, but it is very expensive and not suitable for general use. In addition, a composite film obtained by coating a film of polyester or the like with an epoxy resin or a thermosetting imide resin (Japanese Patent Laid-Open No. 4-101839) has been studied in part, but it is flexible, heat resistant, and further thermosetting. Therefore, there is a problem that a manufacturing cost is required because a long heating process is required.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides heat resistance while maintaining flexibility of a general-purpose resin film, and enables use at 150 ° C. or higher, which has been difficult with conventional general-purpose resin films. Further, the present invention intends to provide a heat-resistant composite film having a photocurable ability that allows the cured layer to be cured in a short time and excellent in workability, and a method for producing the same.

[0004]

The present invention provides a heat-resistant composite film comprising a surface of a thermoplastic film and a cured layer of a photocurable resin composition in which the following components (A) to (D) are blended in the following proportions. Is provided. Component (A): A carboxylic acid derived from an acid anhydride in the product of an aromatic tetracarboxylic dianhydride and an alcohol having a carbon-carbon double bond that can be polymerized by active energy rays.
For the esterification reaction under the condition that the group remains
100 parts by weight of esterification reaction product obtained (B) component: 1-2 mol per 1 mol of aromatic tetracarboxylic dianhydride constituting the aliphatic diamine (A) component that reacts with the (A) component Component (C): 1.1 to 10 parts by weight of photopolymerization initiator or photosensitizer (D) Component: 10 to 1800 parts by weight of polar solvent.

The thermoplastic film used in the present invention is not limited at all and any film can be used. Specific examples thereof include polyester resin films, polyolefin resin films such as polyethylene and polypropylene, and engineering resin films such as polyether ketone and polyphenylene sulfide.
Among these, polyester film is mechanical strength,
It is particularly preferable because it has excellent solvent resistance and appropriate stiffness.

The component (A) in the photocurable resin composition used in the present invention is a product of an aromatic tetracarboxylic dianhydride and an alcohol having a carbon-carbon double bond polymerizable by an active energy ray. It is a compound obtained by carrying out an esterification reaction under conditions such that a carboxylic acid group derived from an acid anhydride remains therein. As the esterification reaction product, 1 mol of an aromatic tetracarboxylic dianhydride is reacted with 2 mol of an alcohol having a carbon-carbon double bond which can be polymerized by an active energy ray to form an ester bond in the molecule. And a compound having a residual carboxylic acid group, that is, a product having two half-esters in the molecule is preferable. Examples of the aromatic tetracarboxylic dianhydride used include pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4 ′
-Benzophenone tetracarboxylic dianhydride and the like. In addition, one kind or a mixture of two or more kinds may be used.

Carbon that can be polymerized by active energy rays
As the alcohol having a carbon double bond, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2
-Hydroxypropyl acrylate, polyethylene glycol modified methacrylate, polyethylene modified acrylate, polypropylene glycol modified methacrylate,
Examples thereof include polypropylene-modified acrylate and allyl alcohol. Among these, 2-hydroxyethyl methacrylate and allyl alcohol are preferable. In addition, in use, one kind or a mixture of two or more kinds may be used.

The esterification reaction of an aromatic tetracarboxylic dianhydride with an alcohol having a carbon-carbon double bond capable of being polymerized by an active energy ray is usually carried out with respect to 1 mol of the aromatic tetracarboxylic dianhydride. Alcohol having a carbon-carbon double bond that can be polymerized by an active energy ray is blended in an excess amount of 2 to 4 mol, preferably 2 to 3 mol, without solvent or as a polar solvent of component (D) described later. It is carried out by heating to 50 to 150 ° C. and heating and stirring for 10 minutes to 2 hours. As a result, a product having two half-esters in the molecule is obtained. (D)
When the reaction of the component in a polar solvent is performed, the concentration of the polar solvent of the component (D) is 10 to 1800 parts by weight with respect to 100 parts by weight of the aromatic tetracarboxylic dianhydride. Depending on the reaction conditions, the remaining carboxylic acid is esterified to form tri- and tetra-esters, but the proportion thereof is preferably 10 mol% or less of the obtained ester.

The obtained esterification reaction product is a product having two half-esters in the molecule or a mixture containing the ester and tri- and tetra-esters, alcohol used in excess, and the like. The obtained esterification reaction product may be used as it is as the component (A) or may be used in the molecule.
A product having one half ester is isolated (A)
You may use it as an ingredient.

[0010] Component (B) aliphatic diamines of the component (A)
Which can react with the esterification reaction product of hexamethylenediamine, dodecamethylenediamine, ethylenediamine, 3,9-bis (3-aminopropyl) -2,
4,8,10-Tetraoxaspiro [5,5] -undecane, 3,9-bis (3-aminoethyl) -2,4
8,10-Tetraoxaspiro [5,5] -undecane, 3,9-bis (3-aminobutyl) -2,4,8,
10-tetraoxaspiro [5,5] -undecane and the like can be mentioned. In addition, in use, one kind or a mixture of two or more kinds may be used. The compounding ratio is 1 to 2 mol with respect to 1 mol of the aromatic tetracarboxylic dianhydride which is a raw material of the esterification reaction product of the component (A). When the component (B) is small, the cured product becomes brittle, and when it is large, the curability is deteriorated.

The photopolymerization initiator of the component (C) is 1-phenyl-2-hydroxy-2-methylpropan-1-one,
Acetophenone compounds such as 1-hydroxycyclohexyl phenyl ketone, 4-diphenoxydichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzophenone, benzoylbenzoic acid Examples thereof include benzophenone compounds such as methyl, 4-phenylbenzophenone, hydroxybenzophenone, and 3,3′-dimethyl-4-methoxybenzophenone. Among these, the preferred photopolymerization initiator is 1-phenyl-
2-hydroxy-2-methylpropan-1-one, 1-
Hydroxycyclohexyl phenyl ketone, benzophenone and benzoyl methyl benzoate. These may be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is 10 parts of the component (B).
0.1 to 10 parts by weight is desirable with respect to 0 parts by weight. 0.
If it is less than 1 part by weight, the uncured portion remains because the amount added is too small, and if it exceeds 10 parts by weight, the photopolymerization initiator in the system lowers the cured film strength, which is not preferable. When a photosensitizer is used, it is used during curing acceleration, and specifically, n-butylamine, triethylamine, N-methyldiethanolamine, triethyl-n-butylphosphine, diethylaminoethylmethacrylate, p-dimethylaminoethylbenzoate, 2-Dimethylaminoethyl benzoate and the like can be mentioned, but when used, one kind or a mixture of two or more kinds may be used. The amount added is the same as or less than that of the photopolymerization initiator.

The polar solvent of the component (D) is selected from the above (A) to (A).
An organic solvent that dissolves the component (C), and specifically,
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide,
An aprotic polar solvent such as hexamethylphosphoramide, the above alcohols, and alcohols such as ethylene glycol mono-substituted ether and polyethylene glycol mono-substituted ether can be used. Of these, N, N-dimethylformamide or N, N-dimethylacetamide is preferred from the viewpoints of workability, reactivity, stability and cost.

The amount of solvent used is such that the solid content is 10 to 90 wt.
From the viewpoint of workability, it is preferable to mix them so as to be%.
When the polar solvent of the component (D) is used in the esterification reaction for synthesizing the component (A) and the esterification reaction product is used as it is as a composition without isolation (D)
The concentration of the photocurable resin composition of the present invention is adjusted by adding or distilling off the polar solvent as a component. By adjusting the solid content concentration, it is possible to adjust the solution viscosity and the thickness of the coating film when the curable resin composition is applied to the film.

The photocurable resin solution composition in the present invention may contain various additives such as an adhesion aid, an inhibitor, a leveling agent and the like. A photocurable resin composition containing the above components (A) to (D) is applied to a thermoplastic film, dried to remove the solvent, and irradiated with active energy rays and heated to form a heat-resistant composite film. can do.

As the method for applying the photocurable resin composition, a dipping method, a casting method, a bar coater method, a screen printing method or the like can be used. Drying conditions vary depending on the solvent used, but are 50 to 200 ° C., preferably 80 to 150 ° C.
Dry for 10 minutes to 2 hours.

Photocuring is performed under irradiation of active energy rays.
Done in. The atmosphere for irradiating with active energy rays is
Either in normal air or in an inert gas atmosphere
Yes. Ultraviolet rays and electron beams are available as active energy rays.
It As a light source of ultraviolet rays, chemical lamps, xenon
Lamp, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury
Emitted from lamps, metal halide lamps, etc.
10 to 500 mj / cm ² , Preferably 30-200
mj / cm² The ultraviolet rays that have the energy of
It

As the electron beam, Cockloft-Walton type, Van de Graaff type, resonance transformer type, insulating core transformer type,
50 to 100 KeV, preferably 1 emitted from various electron beam accelerators such as direct type, dynamitron type and high frequency type.
An electron beam having an energy of 00 to 500 KeV is used. During or after the photo-curing, heat-curing is carried out to carry out imidization and removal of residual solvent, but it is preferable to carry out at the time of photo-curing from the viewpoint of workability. Heating is 100-200
It is carried out at 10 ° C. for 10 minutes to 2 hours.

As the constitution of the composite film, a cured layer of the photocurable resin composition is formed on one side or both sides of the thermoplastic film. Although the thickness of the thermoplastic film is not particularly limited, it is generally 25 to 25.
The one having a thickness of 100 μm is used. Moreover, the thickness of the cured layer of the photocurable resin composition is not particularly limited, but is 5 to 100.
μm is preferred. If it is 5 μm or less, the effect of improving the heat resistance is small, and if it is 100 μm or more, the flexibility is lowered.

[0020]

EXAMPLES The present invention will now be described in more detail based on examples. [Example 1] 3,3 'in a 100 ml eggplant flask,
4,4'-benzophenone tetracarboxylic acid diallyl ester 4.23 g, N, N-dimethylformamide 2.
Charged 82 g, 3,9-bis (3-aminopropyl)
-2,4,8,10-Tetraoxaspiro [5,5]-
A solution of 1.77 g of undecane and 1.18 g of N, N-dimethylformamide was added, and then 1-phenyl-2-hydroxy-2-methylpropan-1-one 0.
1 g was added to obtain a photocurable resin composition solution.

The surface of this solution was sanded.
A 0 μm polyethylene terephthalate (hereinafter abbreviated as “pet”) film was cast on one side using a bar coater method, dried at 80 ° C. for 5 minutes and then at 150 ° C. for 5 minutes, and then dried.
A resin layer of 5 μm was formed. Then, the same treatment is applied to the other surface of the pet film, and the film is cured by irradiating it with ultraviolet rays for 10 minutes in an atmosphere of 150 ° C. from a height of 40 cm from the film with a high pressure mercury lamp with an output of 80 W / cm. Then, a composite film having a yellowish brown cured layer of a photocurable resin was obtained. The characteristics of the obtained film are shown in Table 1.

[Second Embodiment] Same as the first embodiment.
Hexamethylenediamine 0.9 was added to a solution prepared by adding 3.4 g of N, N-dimethylformamide to 5.1 g of 3 ', 4,4'-benzophenone tetracarboxylic acid diallyl ester.
g and N, N-dimethylformamide (0.6 g) were added to the solution, and then 1-phenyl-2-hydroxy-2 was added.
-Methylpropan-1-one (0.1 g) was added to obtain a photocurable resin composition solution.

Using this solution, the same operation as in Example 1 was carried out to obtain a composite film having a yellow-brown cured layer of a photocurable resin. The characteristics of the obtained film are shown in Table 1. [Embodiment 3] Same as Embodiment 1, 3, 3 ', 4, 4'
-3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro was added to a solution prepared by adding 3.04 g of N, N-dimethylformamide to 4.56 g of dimethacryloyloxyethyl benzophenonetetracarboxylate. A solution of 1.77 g of [5,5] -undecane and 1.43 g of N, N-dimethylformamide was added, and then 1-phenyl-2-hydroxy-2-methylpropane-
0.1 g of 1-one was added to obtain a photocurable resin composition solution.

Using this solution, the same operation as in Example 1 was performed to obtain a composite film having a hardened layer of a yellowish brown photocurable resin. The characteristics of the obtained film are shown in Table 1. Example 4 In the same manner as in Example 1, 3,9-bis (3-aminopropyl) -2,4 was added to a solution of 3.88 g of pyromellitic acid diallyl ester and 2.59 g of N, N-dimethylformamide. , 8,10-Tetraoxaspiro [5,5] -undecane (2.12 g) and N, N-dimethylformamide (1.41 g) were added to the solution, and then 1-phenyl-2-hydroxy-2-methylpropane-
0.1 g of 1-one was added to obtain a photocurable resin composition solution. Using this solution, the same operation as in Example 1 was performed to obtain a composite film having a yellow-brown cured layer of a photocurable resin. The characteristics of the obtained film are shown in Table 1.

[Embodiment 5] Similar to Embodiment 1,
To a solution prepared by adding 2.77 g of N, N-dimethylformamide to 4.15 g of 3 ', 4,4'-biphenyltetracarboxylic acid diallyl ester was added 3,9-bis (3-aminopropyl) -2,4,8, A solution of 1.85 g of 10-tetraoxaspiro [5,5] -undecane and 1.23 g of N, N-dimethylformamide was added, and then 1-phenyl-2-hydroxy-2-methylpropane-
0.1 g of 1-one was added to obtain a photocurable resin composition solution.

Using this solution, the same operation as in Example 1 was carried out to obtain a composite film having a cured layer of a yellowish brown photocurable resin. The characteristics of the obtained film are shown in Table 1. Comparative Example The pet film used in Example 1 was evaluated as it was. The results are shown in Table 1.

[0027]

[Table 1]

[0028]

The heat-resistant composite film according to the present invention imparts heat resistance while maintaining the flexibility of a general-purpose resin film,
It enables use at 150 ° C. or higher, which was difficult with conventional general-purpose resin films, and has excellent workability because the cured layer has a photo-curing ability that can be cured in a short time.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-55-25404 (JP, A) JP-A-63-312377 (JP, A) JP-A-59-30809 (JP, A) JP-A-57- 209951 (JP, A) JP 3-223316 (JP, A) JP 56-151746 (JP, A) JP 3-247672 (JP, A) JP 61-36335 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09D 1/00-201/10 B32B 27/36 C08F 6/00-246/00

Claims (4)

(57) [Claims] 1. The following (A) to the surface of the thermoplastic film:
A heat-resistant composite film provided with a cured layer of a photocurable resin composition containing the component (D) in the following proportions. Component (A): A carboxylic acid derived from an acid anhydride in the product of an aromatic tetracarboxylic dianhydride and an alcohol having a carbon-carbon double bond that can be polymerized by active energy rays.
For the esterification reaction under the condition that the group remains
100 parts by weight of esterification reaction product obtained (B) component: 1-2 mol per 1 mol of aromatic tetracarboxylic dianhydride constituting the aliphatic diamine (A) component that reacts with the (A) component Component (C): 0.1 to 10 parts by weight of photopolymerization initiator or photosensitizer (D) Component: 10 to 1800 parts by weight of polar solvent. 2. The heat resistant composite film according to claim 1, wherein the esterification reaction product of the component (A) has two half-esters in the molecule. 3. The alcohol constituting the component (A) is 2-
The heat resistant composite film according to claim 1, which is selected from hydroxyethyl methacrylate and allyl alcohol. 4. The heat resistant composite film according to claim 1, wherein the thermoplastic film is a polyester film.