JPH0410618B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive composition containing glycol diacrylate or methacrylate (hereinafter abbreviated as (meth)acrylate) or a low polymer thereof as an active ingredient. For more details 2
- 1 selected from methylpropylene glycol di(meth)acrylate or its low polymer;
The present invention relates to a photosensitive composition containing a species or a mixture of two or more species as an active ingredient.

Conventionally, liquids with high boiling points have been widely used as photosensitive polymer monomers because they are easy to handle at room temperature and pressure, and have low flash points and toxicity.
And those with good curability are selected. Polyfunctional monomers having two or more unsaturated groups in one molecule and low polymers thereof are usually used as the above-mentioned monomers satisfying such conditions. Most of the unsaturated groups mentioned above are ethylenically unsaturated groups, and photosensitive compositions made of polyfunctional monomers or low polymers that use ethylenically unsaturated groups as functional groups have been studied for a long time, and there are many types. Typical examples of polyfunctional monomers include acrylic esters of polyhydric alcohols, polyacrylic esters linked by urethane bonds, unsaturated esters of polycarboxylic acids, and polyunsaturated acid amides linked by amide bonds. It is something like that. Among them, most of the acrylic esters of polyhydric alcohols are liquids with high boiling points and photopolymerize themselves.
Although it cures in a dimensional manner, it forms an excellent cured film when dissolved with other polymeric substances (hereinafter referred to as filling polymeric compounds), so it is widely used as a photosensitive composition in photoresists, paints, ultraviolet curing inks, etc. has been done.

Generally, acrylic acid or methacrylic acid esters of polyhydric alcohols are synthesized by reacting acrylic acid or methacrylic acid with polyhydric alcohols. The polyhydric alcohols known so far include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol,
Neopentyl glycol, 1,6-hexamethylene glycol, trimethylolpropane, pentaerythritol, etc. are available, but in order to obtain a polyfunctional acrylic acid or methacrylic acid ester that is most suitable for various uses as a photosensitive composition, the above-mentioned The type of polyhydric alcohol must be selected carefully.

As a result of intensive research to expand the range of selection, the present inventors found that 2-methylpropylene glycol di(meth)acrylate, a new compound synthesized using 2-methylpropylene glycol as a polyhydric alcohol, or its lower A photosensitive composition containing a polymer as an active ingredient has a fast curing speed,
The inventors have discovered that when used as a photoresist, images with extremely high resolution can be formed, leading to the present invention.

That is, the present invention provides 2-methylpropylene glycol di(meth)acrylate represented by the formula () or a low polymer thereof (preferably with a degree of polymerization of 2 to 2).
This is a photosensitive composition containing as an active ingredient one type or a mixture of two or more types selected from 5).

(R in the formula is hydrogen or methyl group) 2-Methylpropylene glycol, which is the glycol component of 2-methylpropylene glycol di(meth)acrylate according to the present invention, can be produced industrially by oxidation reaction of isobutene or oxo reaction of allyl alcohol. However, because the chemical structure has a monovalent methyl group at the 2nd-position carbon atom, it is asymmetrical with respect to the main chain of the molecule, and the hydroxyl groups at both ends are both primary, so it is extremely difficult to manufacture. It is a glycol with characteristics such as high chemical reactivity.

In general, methods for synthesizing glycol di(meth)acrylate include (1) dehydrochlorination reaction between an acid chloride of acrylic acid or methacrylic acid and glycol, and (2) a reaction between a glycol monoacrylate derivative and an acid chloride of acrylic acid or methacrylic acid. Synthesis methods include dehydrochlorination reaction, (3) transesterification reaction between a lower alkyl ester of acrylic acid or methacrylic acid and glycol, and (4) direct dehydration reaction between acrylic acid or methacrylic acid and glycol.

The 2-methylpropylene glycol di(meth)acrylate of the present invention is the above-mentioned (1), (2), (3) and
Although it can be synthesized by any of the reactions in (4), as an example, specifically speaking about the reaction in (1), 2
- Methylpropylene glycol and 2 times the mole of pyridine or a tertiary amine such as triethylamine are stored in a reactor equipped with stirring blades, or aromatic hydrocarbons such as ether, benzene, toluene, xylene, hexane, cyclohexane, etc. Pour into a solvent such as aliphatic or alicyclic hydrocarbons, and slowly add 2-methylpropylene glycol while stirring and maintaining the temperature at 0 to 10°C.
Double the molar amount of acrylic acid chloride or methacrylic acid chloride is added dropwise. After sufficient reaction for 5 to 8 hours after the addition, the ammonium hydrochloride produced by filtration is removed from the reaction mixture. Next, the solvent is distilled off from the liquid under reduced pressure, and the residue is then vacuum distilled to obtain the objective 2-methylpropylene glycol di(meth)acrylate as a colorless and transparent liquid. The 2-methylpropylene glycol di(meth)acrylate low polymer can also be obtained by polymerization using a very small amount of a general polymerization catalyst.
It is preferable to carry out thermal polymerization without a catalyst at 50 to 100°C for about 15 to 60 minutes; if the degree of polymerization is increased too much, the compound itself will crosslink and harden, making it unsuitable as a compound constituting a photosensitive composition. The degree of polymerization is preferably up to 5, more preferably up to 3.

Generally, when acrylic acid or methacrylic ester of a polyhydric alcohol or a low polymer thereof is used as a photopolymerizable compound in a photoresist, the compound, a filler polymer compound having film-forming ability, and an appropriate sensitizer, dye, etc. After uniformly dissolving in an organic solvent, the solution is applied to a suitable thickness on a substrate and the solvent is removed to form a so-called photosensitive resin film, which is then irradiated with ultraviolet rays to reproduce images using a photographic method. is being carried out.

However, one or two selected from 2-methylpropylene glycol di(meth)acrylate or its low polymer obtained by the present invention.
For example, when a photosensitive composition containing a mixture of more than one species as an active ingredient is used as a photoresist,
Surprisingly, the curing speed was fast and images with extremely high resolution were obtained. Although the reason for this has not yet been elucidated, the following two points can be considered. In other words, in 2-methylpropylene glycol constituting 2-methylpropylene glycol diacrylate or dimethacrylate, (1) polarity effect due to the electron pushing action of the methyl group bonded to the 2-position carbon atom (2) due to (1) However, it is expected that stable tertiary radicals will be generated due to the elimination effect of the hydrogen atom at the 2-position, further enhancing the crosslinking effect. That is, although it can have only two photopolymerizable terminal unsaturated groups, it is thought to act as if it were a trifunctional unsaturated compound. The amount of 2-methylpropylene glycol di(meth)acrylate or a mixture of two or more selected from 2-methylpropylene glycol di(meth)acrylate or a low polymer thereof to be blended into the photosensitive composition of the present invention is determined excluding the solvent in the composition. 20 to 80 as solid content
% by weight is preferred, more preferably 30-60% by weight
It is.

Further, as the filled polymer compound that can be incorporated into the photosensitive composition of the present invention, homopolymers and copolymers of methyl methacrylate are used. In addition, as a sensitizer, Michler's ketone, N,N'-tetraethyl-4,4'-diaminobenzophenone,
5-nitroacenaphthene, 1,2-benzanthraquinone, N-acetyl-4-nitronaphthylamine, benzyl, benzoin, α-naphthoquinone, 1-nitropyrene, 9-fluorenone, 1,
8-phthaloylnaphthalene and the like are used. Furthermore, one or a mixture of two or more selected from the 2-methylpropylene glycol di(meth)acrylate of the present invention and low polymers thereof, and other well-known polyfunctional monomers. It goes without saying that a similarly clear image with good resolution can be obtained by mixing a suitable proportion of the compound and a low polymer thereof such as pentaerythritol triacrylate or trimethylolpropane trimethacrylate.

The present invention will be explained in detail below using synthesis examples and examples, but the present invention is not limited by these. In addition, parts in the examples mean parts by weight, and the infrared absorption spectrum was obtained using IRA-2 manufactured by JASCO Corporation.
Type, nuclear magnetic resonance spectrum is C- manufactured by JEOL Ltd.
Measured using 60HL model.

Synthesis Example 1 50 parts of 2-methylpropylene glycol and 101 parts of triethylamine were vigorously stirred using 101 parts of dry ether as a solvent, and while cooling the reaction vessel with ice water to maintain the reaction temperature at 0 to 10°C, Slowly drop 100 parts of acid chloride.
After the dropwise addition was completed, stirring was continued for 5 hours at room temperature and after confirming that the reaction had progressed sufficiently, the triethylamine hydrochloride was separated from the reaction mixture, the solution was washed with water until it became neutral, and dried over anhydrous magnesium sulfate. After filtering, the solvent was distilled off under reduced pressure to obtain 102 parts of a pale yellow liquid substance. Five parts of cuprous chloride, known as a polymerization inhibitor, was added to this substance and vacuum distilled, yielding 90 parts of a colorless and transparent liquid substance (71
℃/3mmHg).

The structural formula of the liquid substance thus obtained was confirmed to be 2-methylpropylene glycol diacrylate by elemental analysis, infrared absorption spectrum, and nuclear magnetic resonance spectrum.

Synthesis Example 2 50 parts of 2-methylpropylene glycol and 116 parts of triethylamine were stirred vigorously using 100 parts of dry ether as a solvent, and while cooling the reaction vessel with ice water to maintain the reaction temperature at 0 to 5°C, methacrylic acid chloride was added. Slowly drip 116 parts. After the dropwise addition was completed, stirring was continued at room temperature for 5 hours to confirm that the reaction had progressed sufficiently. After that, the triethylamine hydrochloride was separated from the reaction mixture, the solution was washed with water until it became neutral, and dried over anhydrous magnesium sulfate. After filtering, the solvent was distilled off under reduced pressure to obtain 110 parts of a pale yellow liquid substance. Five parts of cuprous chloride, which is known as a polymerization inhibitor, was added to this substance and vacuum distilled to obtain 95 parts of a colorless and transparent supporting substance (62°C/2mmHg).

The structural formula of the liquid material thus obtained was confirmed to be 2-methylpropylene glycol dimethacrylate by elemental analysis, infrared absorption spectrum, and nuclear magnetic resonance spectrum.

Synthesis Example 3 100 parts of methyl methacrylate was mixed with 200 parts of dry toluene.
0.7 parts of N,N'-azobisisobutyronitrile, which is well known as a polymerization initiator, was added, and the mixture was reacted at 60° C. for about 5 hours under a nitrogen atmosphere. After the reaction, this was poured into methanol to precipitate a white polymer. After thorough drying, the viscosity was measured using toluene as a solvent and found that [η] = 0.34 (25
℃).

Example 1 10 parts of the compound obtained in Synthesis Example 1 12.5 parts of the polymer compound obtained in Synthesis Example 3 Stir vigorously for 10 minutes to finely disperse the pigment. The coating solution thus obtained was coated using a Meabar coater.
A blue sheet was obtained when it was applied onto a PET film (75 μm) and dried at 60° C. for 5 minutes. The thickness of the coating layer was approximately 5 μm. Next, the photosensitive film thus obtained was placed in close contact with a transparent photographic negative, and then printed using an Oak Jet printer (manufactured by Oak Seisakusho, 2KW mercury lamp) from a distance of 40 cm from a light source.
Exposure was made for 120 seconds. Immediately after exposure, a yellow latent image could be discerned in the light irradiated area. Next, 10 parts of toluene
- When it was developed with a mixed solution consisting of 90 parts of hexane, the compound in the unexposed area was removed from the PET film, and the photocured area became insoluble and remained on the PET film as it was. The resolution thus obtained was 20 μm.

Example 2 10 parts of the compound obtained in Synthesis Example 2 12.5 parts of the polymer compound obtained in Synthesis Example 3 2,6-di(4-azidobenzal)cyclohexane 0.8 parts Crystal violet 0.05 parts Hydroquinone 0.2 parts Tetrachloroethane 50 Part The pigment was dispersed in the above composition liquid in the same manner as in Example 1, and the mixture was applied onto a PFT film and dried.
The thickness of the coating layer was approximately 5 μm. When exposed in the same manner as in Example 1, the latent image developed a reddish-yellow color. When developed with a mixture of 10 parts of tetrachloroethane, 10 parts of toluene, and 80 parts of n-hexane, an extremely good image was obtained. The resolution obtained in this way is
It was 25μm.

Comparative Example 1 10 parts of diethylene glycol diacrylate 12.5 parts of the polymer compound obtained in Synthesis Example 3 It was then applied onto PET film and dried.
The thickness of the coating layer was approximately 5 μm. When exposed in the same manner as in Example 1, a latent image was slightly discernible. Next, the same developer as in Example 1 (10 parts of toluene, n-
When developed with 90 parts of hexane), an image was obtained, but the resolution was approximately 40 μm.

Synthesis Example 4 50 parts of 1,3-butylene glycol and 101 parts of triethylamine were stirred vigorously using 101 parts of dry ether as a solvent, and the reaction vessel was cooled with ice water to maintain the reaction temperature at 0 to 10°C. , slowly drip 100 parts of methacrylic acid chloride.
After the dropwise addition was completed, stirring was continued at room temperature for 6 hours, and after confirming that the reaction had progressed sufficiently, the triethylamine hydrochloride was filtered off from the reaction mixture, the filtrate was washed with water until it became neutral, and then diluted with anhydrous magnesium sulfate. After drying and filtration, the solvent was distilled off under reduced pressure to obtain 100 parts of a pale yellow liquid substance. 3 parts of cuprous chloride, known as a polymerization inhibitor, was added to this substance and vacuum distilled to obtain 85 parts of a colorless, transparent, viscous liquid substance (71°C/3mmHg).

The structural formula of the liquid substance thus obtained was confirmed to be 1,3-butylene glycol dimethacrylate ester by elemental analysis, infrared absorption spectrum, and nuclear magnetic resonance spectrum.

However, compared to Synthesis Example 2, 1,3-
Butylene glycol has a secondary hydroxyl group at one end, and due to steric hindrance of the methyl group, the reaction rate was slow and the yield was poor.

Comparative Example 2 10 parts of 1,3-butylene glycol dimethacrylic ester obtained in Synthesis Example 4 12.5 parts of the polymer compound obtained in Synthesis Example 3 2,6-di(4-azidobenzal)cyclohexanone 0.8 parts Crystal violet 0.05 1 part Hydroquinone 0.05 parts Tetrachloroethane 50 parts Pigment was dispersed in the above composition liquid in the same manner as in Example 1, and the mixture was coated on a PET film and dried.
The thickness of the coating layer was approximately 5 μm. When exposed in the same manner as in Example 1, a latent image was slightly discernible.
Next, the same developer as in Example 1 (10 parts of toluene, n
- 90 parts of hexane), an image was obtained, but the resolution was approximately 47 μm.

The reason why the resolution is inferior to that in Example 2 is that the methine hydrogen attached to the branched methyl group of 1,3-butylene glycol methacrylic ester is extracted by the polymerization initiator, resulting in tertiary carbon radicals. However, it is presumed that this is because the tertiary carbon radical becomes unstable due to the electron absorption effect of the neighboring ester group, resulting in a shortened lifespan and a reduced proportion contributing to the crosslinking reaction.

Claims (1)

[Scope of Claims] 1. 20 to 80% solid content of 2-methylpropylene glycol di(meth)acrylate represented by formula () or a mixture of two or more selected from among its low polymers. A photosensitive composition comprising a filled polymer compound consisting of a single or copolymer of methyl methacrylate and a sensitizer. (R in the formula is hydrogen or methyl group)