JP3422103B2 - Photocurable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable heat-resistant resin composition having excellent heat resistance and workability, which is useful for coating agents, adhesives, paints, laminates, resists and composite materials.

[0002]

2. Description of the Related Art Photocurable resins are widely used in paints, adhesives, printing inks, hard coats and the like. However, the resins used hitherto have low heat resistance, and therefore their use at high temperatures is significantly limited. On the other hand, as a photocurable resin having high heat resistance, by introducing a compound having a carbon-carbon double bond polymerizable by an active energy ray into a carboxyl group of a polyamic acid, which is a polyimide precursor, by ionic or covalent bonding A curable polyimide resin (for example, JP-A-58-120).
636, JP-A-63-99235 and the like) have been proposed.

[0003]

The resin obtained by imparting a photocurable property to the polyimide precursor disclosed in the above publication requires a step of producing the polyimide precursor, though it has a heat resistance improving effect, and further has a photocurable property. There is a problem that it is necessary to carry out post-curing at a high temperature of 200 ° C. or higher in order to carry out post-imidization.

The present invention provides a resin composition which solves the above problems and provides a photocurable resin having excellent heat resistance and workability.

[0005]

The present invention includes the following (A)-
Component (D): Component (A): 100 parts by weight of an esterification reaction product of an aromatic tetracarboxylic dianhydride and an alcohol having a carbon-carbon double bond that can be polymerized by an active energy ray. Component (B): Aliphatic diamine 1-2 mol (C) component: 0.1 to 10 parts by weight of photopolymerization initiator or photosensitizer (D) component: polar solvent based on the number of moles of the aromatic tetracarboxylic dianhydride. The present invention provides a photocurable resin composition containing 10 to 1800 parts by weight in the above proportion.

The photocurable resin obtained from the composition of the present invention is excellent in heat resistance and does not require a step of producing a polyimide precursor, and further, it is 200 ° C. or lower at the same time as or before and after the photocuring. Since a polyimide can be produced by curing at a relatively low temperature, a photocurable resin having excellent workability is provided.

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 which 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.

As the aliphatic diamine as the component (B), hexamethylene diamine, dodecamethylene diamine, ethylene diamine, 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). (B)
When the amount of the component is small, the cured product becomes brittle, and when it is large, the curability is lowered.

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 amount of addition is too small to leave an uncured portion. 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, the polar solvent of the component (D) is added or distilled off. By doing so, the concentration of the photocurable resin composition of the present invention is adjusted. 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 according to the present invention may contain various additives such as an adhesion aid, an inhibitor, a leveling agent and the like. The cured product of the photocurable resin solution composition of the present invention is used as a heat resistant coating film, an adhesive, a paint or a photoresist. The cured product is obtained by applying the photocurable resin solution composition onto a substrate, drying the solvent to remove the solvent, and irradiating with active energy rays and heating.

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.

The thickness of the cured layer of the photocurable resin composition is not particularly limited, but is preferably 5 to 100 μm. If it is 5 μm or less, the effect of improving heat resistance is small, and 100 μm
When it is m or more, flexibility is lowered.

[0021]

EXAMPLES The present invention will be described in more detail based on the following examples. [Example 1] 3,3 'in a 100 ml eggplant flask,
3,4 g of 4,4′-benzophenone tetracarboxylic acid dianhydride, 1.12 g of allyl alcohol, and 2.82 g of N, N-dimethylformamide were charged, and the eggplant flask was attached to the rotary evaporator. After substitution, the temperature was raised to 80 ° C., and the reaction was carried out at the same temperature for 2 hours to synthesize a diallyl ester. 3,9-bis (3-aminopropyl) -2,4,8,1 was added to this solution.
0-Tetraoxaspiro [5,5] -undecane 1.7
A solution prepared by adding 1.18 g of N, N-dimethylformamide to 7 g was added, and then 0.1 g of 1-phenyl-2-hydroxy-2-methylpropan-1-one was added to obtain a photocurable resin composition solution. did.

This solution was uniformly cast on an aluminum plate using a 25 μm applicator, and the solution was cast at 80 ° C. for 5 hours.
Min, then dried at 150 ° C for 5 minutes, and then in an atmosphere of 150 ° C, output from a height of 40 cm from the aluminum plate 80 W /
It was irradiated with ultraviolet rays for 10 minutes by a high pressure mercury lamp of cm to cure it, and a yellowish brown tough coating film was obtained. Table 1 shows the storage stability of the solution and the characteristics of the coating film.

[Embodiment 2] In Embodiment 1, 3, 3 ', 4,
4'-benzophenone tetracarboxylic dianhydride 3.
11 g 3.75 g, allyl alcohol 1.12 g 1.35 g, N, N-dimethylformamide 2.82 g
The same operation was performed except that the amount of was changed to 3.4 g to synthesize diallyl ester. A solution of 0.9 g of hexamethylenediamine and 0.6 g of N, N-dimethylformamide was added to this solution, and then 0.1 g of 1-phenyl-2-hydroxy-2-methylpropan-1-one was added. A photocurable resin composition solution was prepared. Using this solution, the same operation as in Example 1 was carried out to obtain a yellowish brown coating film. The characteristics of the obtained coating film are shown in Table 1.

[Example 3] 1.12 g of allyl alcohol in Example 1 was mixed with 2.04 of hydroxyethyl methacrylate.
2.52 g of 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 3.11 g in place of g, N,
Diester was synthesized in the same manner except that N-dimethylformamide (2.82 g) was replaced with 3.04 g, the temperature was changed to 110 ° C., and the time was changed to 1.5 hours. 3,9-bis (3-aminopropyl) -2,4,8,1 was added to this solution.
0-Tetraoxaspiro [5,5] -undecane 1.7
A solution obtained by adding 1.43 g of N, N-dimethylformamide to 7 g was added, and then 0.1 g of 1-phenyl-2-hydroxy-2-methylpropan-1-one was added to obtain a photocurable resin composition solution. did. Example 1 using this solution
The same operation as above was performed to obtain a yellowish brown coating film. The characteristics of the obtained coating film are shown in Table 1.

[Embodiment 4] 3, 3 ', 4, of Embodiment 1
4'-benzophenone tetracarboxylic dianhydride 3.
The same procedure was repeated except that 11 g was replaced with 2.53 g of pyromellitic dianhydride, 1.12 g of allyl alcohol was replaced with 1.35 g, and 2.82 g of N, N-dimethylformamide was replaced with 2.59 g. Was synthesized. 3,9-bis (3-aminopropyl) -2,4, was added to this solution.
2.10 g of 8,10-tetraoxaspiro [5,5] -undecane in 1.41 g of N, N-dimethylformamide
Was added, and then 0.1 g of 1-phenyl-2-hydroxy-2-methylpropan-1-one was added to prepare a photocurable resin composition solution. Using this solution, the same operation as in Example 1 was carried out to obtain a yellowish brown coating film. The characteristics of the obtained coating film are shown in Table 1.

[Embodiment 5] 3, 3 ', 4, of Embodiment 1
4'-benzophenone tetracarboxylic dianhydride 3.
11 g of biphenyl tetracarboxylic dianhydride 2.98
Instead of g, 1.12 g of allyl alcohol 1.12 g,
2.77 g of N, N-dimethylformamide 2.82 g
A diallyl ester was synthesized by the same operation except that To this solution was added 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5].
5] -Undecane (1.85 g) was mixed with N, N-dimethylformamide (1.23 g) to prepare a solution, and then 1-phenyl-2-hydroxy-2-methylpropan-1-one (0.1 g) was added to perform photocuring. Resin composition solution. Using this solution, the same operation as in Example 1 was carried out to obtain a yellowish brown coating film. The characteristics of the obtained coating film are shown in Table 1.

[0027]

[Table 1] * 1: Points at which insoluble analysis occurs and viscosity changes * 2: DMA method Tan δ peak * 3: JIS K5400 * 4: Points at which the appearance of the coating film becomes abnormal when immersed in molten solder at 260 ° C

[0028]

The photocurable resin obtained from the composition of the present invention is excellent in heat resistance, does not require a step of producing a polyimide precursor, and is 200 times before or after the photocuring. Since a polyimide can be produced by curing at a relatively low temperature of ℃ or less, it provides a photocurable resin having excellent workability.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-7-238168 (JP, A) JP-A-6-80780 (JP, A) JP-A-6-80776 (JP, A) JP-A-3- 233457 (JP, A) JP-A-60-26030 (JP, A) JP-A-57-137354 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 73/00-73 / 26

Claims (3)

(57) [Claims] 1. Component (A): 100 parts by weight of an esterification reaction product of an aromatic tetracarboxylic dianhydride and an alcohol having a carbon-carbon double bond polymerizable by an active energy ray. Component (B): Aliphatic diamine 1-2 mol (C) component: 0.1 to 10 parts by weight of photopolymerization initiator or photosensitizer (D) component: polar solvent based on the number of moles of the aromatic tetracarboxylic dianhydride. 10-1800 parts by weight A photocurable resin composition containing the above components in the above proportions. 2. The photocurable resin composition according to claim 1, wherein the esterification reaction product of the component (A) has two half-esters in the molecule. 3. The photocurable resin composition according to claim 1, wherein the alcohol as the component (A) is selected from 2-hydroxyethyl methacrylate or allyl alcohol.