JPH0641547B2 - Reactive polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a reactive polymer composition. More specifically, the present invention relates to a reactive polymer composition which becomes extremely insoluble in a solvent by irradiating with light having a relatively long wavelength such as visible light to cause a crosslinking reaction very quickly.

[Conventional technology]

Reactive polymers are used in many applications including photoresists, such as acrylic acid-based polymers and styrene-based polymers. At that time, examples are known in which an epoxy group, a halogen group, a carbon-carbon double bond, or the like is used as a crosslinkable functional group.

[Problems to be solved by the invention]

Since the above-mentioned functional groups are not so high in photosensitivity, crosslinking with visible light is unlikely to occur.

Therefore, for the purpose of reacting with visible light having a relatively long wavelength, a dye or the like is blended, the dye is excited, and a reactive functional group is excited by energy transfer. However, the effect was not sufficient. In addition, it is possible to react the reactive functional group by irradiation with long-wavelength visible light by forming the reactive functional group itself into a complex structure having a relatively long conjugated system, but it is difficult to manufacture it. There was a problem.

[Means for solving problems]

The present inventors diligently studied a method for solving the above problems, found that the above problems can be solved by combining a specific polymer and a specific dye, and completed the present invention.

That is, the present invention is obtained by radical polymerization or anion polymerization of divinylbenzene and / or diisopropenylbenzene and at least one other polymerizable monomer selected from styrene, α-methylstyrene and derivatives thereof. Polymer containing vinyl group and / or isopropenyl group-containing monomer in a molar ratio of 0.02 to 0.40 of all monomer units and crystal violet, malachite green, safranine-T, rhodamine-B, basic fuchsin, Hoffmans The reactive polymer composition comprises at least one dye selected from the group consisting of violet and methylene blue in a ratio of 0.0001 to 0.01 with respect to the polymer 1.

The other polymerizable monomer used in producing the polymer constituting the composition of the present invention is at least one selected from styrene, α-methylstyrene and derivatives thereof.

As the above-mentioned polymerization reaction method of the polymerizable monomer and divinylbenzene and 1 or diisopropenylbenzene, a radical polymerization method and an anionic polymerization method are adopted.

The content of vinyl group- and / or isopropenyl group-containing monomer units in the polymer is 0.02 to 0.40 mol ratio, preferably 0.05 to 0.40 mol ratio, based on the total monomer units.

The molecular weight of the polymer is not particularly limited, but is preferably 0.05 as the intrinsic viscosity number measured in a toluene solution at 30 ° C.
As described above, it is preferably 0.1 to 2.0 in terms of handling such as reactivity and coating property and moldability of the reactive polymer.

As the dye constituting the composition of the present invention, crystal violet, malachite green, rhodamine-B, safranin-T, Hoffman's violet, methylene blue and basic fuchsin are used, and among them, crystal violet is preferable from the viewpoint of reactivity. The use ratio of the dye to the polymer is 0.0001 to 0.01 wt ratio, preferably
The ratio is 0.001 to 0.01 wt.

The composition of the present invention is obtained by mixing the above-mentioned polymer and dye, and the mixing method is not particularly limited. It is easy to uniformly mix the polymer and the dye by dissolving and mixing them in a solvent such as a halogenated hydrocarbon compound, and the solvent used is removed by evaporation, which is a preferred method.

The composition of the present invention is prepared by dissolving and mixing it in a solvent such as the above-mentioned halogenated hydrocarbon compound or by dissolving the composition in an appropriate solvent, coating it on a necessary place such as a substrate, and then irradiating it to react It can be used as a polymerizable polymer composition.

〔The invention's effect〕

The composition of the present invention extremely easily undergoes a crosslinking reaction by irradiation with light having a relatively weak energy such as visible light, and is insolubilized in a solvent. Therefore, it can be suitably used for applications such as resists and is industrially valuable. .

〔Example〕

 Hereinafter, the present invention will be further described with reference to examples.

Example 1 Radical copolymerization of styrene and m-diisopropenylbenzene with azobisisobutyronitrile (m-diisopropenylbenzene / styrene 14/86 molar ratio, monomer concentration 30 vol% in toluene solution 70 Polymerized at 30 ° C), the intrinsic viscosity number measured with a toluene solution at 30 ° C was 0.39, 1.0 g of a styrene copolymer containing 0.12 mol ratio of m-isopropenylcumene unit, and 5 mg of crystal violet in 5 ml of chloroform. Dissolved. A glass plate was immersed in this solution to form a thin film, and then vacuum dried at 45 ° C. or lower for 2 hours. The thickness of the thin film was about 20 μm. This thin film was irradiated with a halogen lamp (100 W) using a Toshiba cut filter VY42 from a distance of 20 cm for 2 hours.

Then, it was treated with chloroform, but the coating film was insoluble.

Comparative Example 1 Only the m-isopropenylcumene unit-containing copolymer used in Example 1 was similarly formed into a thin film and then irradiated with a halogen lamp in the same manner as in Example 1, but even after 8 hours, chloroform was completely removed. Dissolved.

Example 2 The same operation as in Example 1 was performed by using Hoffman's violet instead of crystal violet. After irradiation for 2 hours, a part of the film was insolubilized, but 3
It did not melt at all after a while.

Example 3 The same operation as in Example 1 was obtained by the same radical copolymerization,
It was carried out using a copolymer containing 0.35 mol ratio of m-propenylcumene unit (intrinsic viscosity number 0.33).

It was completely insoluble in chloroform after irradiation for 1 hour.

Example 4 α-methylstyrene and divinylbenzene (m- and p-
A mixture of bodies) using α-methylstyrene itself as a solvent,
Divinylbenzene was added in a proportion of 0.18 mol of α-methylstyrene, and azobisisobutyronitrile was used in the same manner as in Example 1 to radically polymerize at 70 ° C. Light irradiation was carried out in the same manner as in Example 1 using a copolymer having an intrinsic viscosity of 0.28 measured in a toluene solution and 0.01 wt% of the basic fuchsin copolymer. After 2 hours of irradiation the coating was insoluble in chloroform.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area H01L 21/027

Claims (1)

[Claims] 1. Obtained by radical polymerization or anion polymerization of divinylbenzene and / or diisopropenylbenzene and at least one other polymerizable monomer selected from styrene, α-methylstyrene and derivatives thereof. Polymer containing vinyl group and / or isopropenyl group-containing monomer in a molar ratio of 0.02 to 0.40 of all monomer units, and crystal violet, malachite green, safranine-
A reactive polymer composition in which at least one dye selected from the group consisting of T, rhodamine-B, basic fuchsin, Hoffman's violet, and methylene blue is used in a ratio of 0.0001 to 0.01 wt% relative to the polymer 1.