JPS58183720A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:The titled composition forming images having improved adhesiveness to bases, comprising an unsaturated monomer as an active ingredient obtained by reaction of a specific glycol, a urethane bond-containing compound having diisocyanate groups at both ends, glycol monoacrylate, etc. CONSTITUTION:2-Methyl-1,3-propylene glycol is reacted with a diisocyanate compound [e.g., 1-methylbenzole-2,4-(2,6,-2,5-,3,5-)diisocyanate, etc.] in the presence of a polymerization inhibitor (e.g., hydroquinone, etc.) at room temperature - about 200 deg.C for several hours, to give a urethane bond-containing monomer or low polymer having diisocyanate groups at both ends, to which glycol monoacrylate or glycol monomethacrylate is added dropwise to give an unsaturated group-containing monomer or lower polymer. A photosensitive resin is obtained using a mixture of the above-mentioned monomers or low polymers as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the desired unsaturated monomer or unsaturated low polymer can be effectively produced by reacting a diisocyanate compound at the end of the inner bed having a certain amount of glycol and urethane bond with glycol monoacrylate or glycol methacrylate. This is related to the photosensitive resin composition as an ingredient. Furthermore, a monomer or a low polymer thereof having a urethane bond with 2-methyl-1,3-propylene glycol and containing a 9-terminal noisocyanate group may be further combined with glycol monoacrylate) or glycol monomethacrylate. The present invention relates to a photosensitive resin composition containing as an active ingredient one type or a mixture of two or more types of unsaturated monomers or unsaturated low polymers obtained by reacting with .

Conventionally, in the field of N-density processing, especially in the field of glint wiring, it has been used as a wear-resistant coating for plating or etching.
It is widely known that photosensitive resins are used for shaping. The properties of the photosensitive resin for forming such a corrosion-resistant film are photosensitive. Examples include excellent W strength, excellent etching resistance and plating resistance, and good adhesion.

Generally, a double-terminated diisocyanate compound containing a glycol component is synthesized by reacting a polyhydric alcohol with a diincyanate compound.

The polyhydric alcohols known so far include ethylene glycol, diethylene glycol, triethylene glycol, tetraethyl/7 glycol, globylene glycol, 1.4$-7' ethylene glycol,
, 4-butylene glycol, neobenzene gelylcol, 1,6-hexamethylene glycol, trimethylolpropane, pentael), etc., but each of them has various uses as a photosensitive resin composition [11] To obtain a double-terminated diisocyanate compound containing the above-mentioned polyhydric alcohol, the IIN range of the above polyhydric alcohol must be carefully selected. The inventors said that)#! Range of choices
! As a result of intensive efforts to expand l, a diisocyanate compound at both ends bonded with 2-methyl-1,5-propylene glycol and urethane was synthesized using 2-methyl-1,δ-propylene glycol as a polyhydric alcohol. Photosensitive resin compositions containing as active ingredients unsaturated monomers or unsaturated low polymers obtained by reacting monomers or low polymers with glycol monoacrylate or glycol monomethacrylate, The inventors have discovered that when used as a photoresist that is exposed to active light such as ultraviolet rays or lasers, it forms images with excellent resolution and extremely good adhesion to film substrates, leading to the present invention.

That is, the present invention involves reacting a monomer or low polymer containing isocyanate groups at both ends obtained by reacting 2-methyl-1,5-propylene glycol with a diisocyanate compound, and further reacting it with glycol monoacrylate or glycol monomethacrylate. This is a photosensitive resin composition containing as an active ingredient one type or a mixture of two or more types of unsaturated monomers or unsaturated low polymers obtained in the following manner.

2-Methyl-1,5-propylene glycol, which is a glycol component of an unsaturated monomer or an unsaturated monomer having a urethane bond proposed in the present invention, can be produced by the oxidation reaction of isobutyne or the suxo reaction of allyl alcohol. However, due to the chemical structure, one methyl group is attached to the foot atom at the 2nd position, so it is asymmetrical and the hydroxyl groups at both ends are both primary. It is a glycol with characteristics such as being extremely chemically reactive.

The general method for preparing the unsaturated monomers or unsaturated oligomers having glycol and urethane bonds according to the present invention is as follows: 1-polymer inhibitors, such as hydroquinone, paramethane diphenol.

The glycol and the diisocyanate compound are heated at 11 to 200 C in the presence of Virogapol.

Preferably, the reaction is carried out at room temperature to 100 CK for several hours.

By this method, monomers or low polymers containing diincyanate groups at both ends and having urethane bonds (#'iz as one polymer) can be easily obtained.

up to but preferably up to 10) can be obtained. Furthermore, by adding glycol monoacrylate (7) or glycol monomethacrylate (7), a monomer or a monomer containing an unsaturated group can be obtained. In the reaction, it is also effective to use inert II solvents such as acetone, methyl ethyl lactone, dimethyl sulfonate, toluene, xylene, and benzene.

It is also possible to gradually introduce the components of the reaction into the reaction in several batches. It is desirable that the hydroxyl groups of the residues in the glycol monoester and the glycol monoester are reacted in a small amount.

Since unreacted glycol monoester generally does not have an adverse effect on photosensitivity, it can be used in a slight excess relative to the diisocyanate.

Usually, it is desirable that the excess ratio of hydroxyl groups is #11096 or higher. After the reaction, if there is a possibility that unreacted incyanate groups remain in the system, it is a common practice to dispose of them with KFi or an active low-boiling alcohol, such as methanol.

Although there is no particular limitation on the diacyane compound used in the present invention, aromatic and aliphatic compounds that react with the tetrahydrone group to form a urethane bond are preferable. Examples of such diisocyanate compounds include:

+, 3′1 mourning is 1.4-phenylene diinocyanate, 1-methylbenzo-2.4- (,2,6-,2
,5-.

s,s-)diincyanate 5L5fucymethylbenzole-2.4-(4,6-)diincyanate, 1
-Ethylbenzo-2,4-diincyanate, naphthalene-1,4-(1,5-12,4-12,7-) diisocyanate, biphenyl-2,4'-(4°4'-diisocyanate, diphenylmethane- 4゜4'-diisocyanate), 2.2'-dimethyldiphenylmethane-
4,4'~diincyanate 1 benzophenone-6,S
'-diisocyanate, ethane diisocyanate, propa/diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, thiodipropyl diisocyanate, and the like. Among these diincyanate compounds, Fi, 1-methylbenzo-2,4-(
2,6+, 2.5-13.5-) diisocyanates.

★9. The glycol monoacrylate or glycol monomethacrylate used in the present invention is not subject to any limitations, but aliphatic ones that easily react with incyanate groups to form urethane bonds are particularly preferred. It is used. For example, 2-hydroxyethyl acrylate, 2-hydroxyethylmethane')
)=, 2-hydroxyethyl acrylate, 2-human p
xyglovir methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolgloban diacrylate)%)
! Examples include J+J techz-rug pandimethacrylate. Generally, unsaturated monomers or unsaturated monomers obtained by reacting polyhydric alcohols, urethane-bonded -terminal diisocyanate, -to compounds, and glycol monoacrylate or glycol monomethacrylate. When using a low polymer as a photopolymerizable compound, it is necessary to add the compound, a filler molecular compound with film-forming ability, and an excessive amount of sensitizer, dye, thermal polymerization inhibitor, etc. to an organic solvent. After solving the problem, the solution was applied to an appropriate thickness on the substrate, the solvent was removed, and a so-called photosensitive resin film was formed. A method has been used to perform the -fII motion using a photographic method by irradiating active light such as ultraviolet rays.

However, 1) a monomer containing both inocyanate groups or a low polymer thereof obtained by reacting the 2-methyl-1,5-propylene glycol of the present invention with a diisocyanate compound is further added to glycol monoacrylate or glycol monomethacrylate. 1 selected from unsaturated monomers or unsaturated low polymers obtained by reacting with
Photosensitive IIM containing a species or a mixture of two or more species as an active ingredient
For example, when a fat composition is used in a photoresist,
Surprisingly, the curing speed was also very low, and an image with extremely good adhesion to the PIT film substrate was obtained.

Although the reason for this has not yet been elucidated, the following may be considered. Sunarichi% 2-
It constitutes an unsaturated monomer or an unsaturated monomer obtained by forming a urethane bond with methyl-1,5-propylene glycol and reacting a nine-end diincyanate compound with glycol monoacrylate or glyco-A monomethacrylate. In 2-methyl-1,3-propylene glycol, there is a polar effect due to the electron pushing action of the methyl group bonded to the 2nd carbon atom, and a hydrogen atom covalently bonded to the same carbon atom as the methyl group (Methine Mizuki). It is expected that multistable Tsuru tertiary radicals will be generated due to the dissociation effect of atoms), further enhancing the crosslinking effect. In other words, although it has only two photopolymerizable wood end unsaturated groups, it is thought to act as if it were a compound with three or more functions.

Examples of the full lambda polymer compound used in the present invention include cylindrical molecular compounds represented by K such as *a polymer and comonomer of methyl methacrylate, cellulose alligator conductor, polyvinyl algol, and noholac *&. . In addition, as a sensitizer, Fiq, N,N'-natraethyl-4,4'-diaminobenzophenone, benzophenone, 5-nitroacenaphthene, 1,2-benzanthraquinone, benzyl, benzoin, sulfur-naphthoquinone, 9- Fluorenone and the like are used. In addition, the urethane bonds of the present invention can be combined with monounsaturated or unsaturated low polymers and other well-known multifunctional unsaturated compounds such as pentaerythritol triacrylate, trimethylolglobin, etc. Even when mixed with trinotacrylate in a large proportion, it has a fast saponification rate and good adhesion. l image can be obtained#
iN of course.

It is desirable that the photosensitive resin composition of the present invention contains a thermal polymerization inhibitor for stability. Derivatives such as 5-butylcatechol, naphthylamine, β-su7tol, and p-torquinone can be mentioned. 4. It is possible to add various plasticizers, dyes, and pigments to apply the photosensitive resin composition to various uses. It is. In addition, when using photosensitive resin compositions, thermosetting resins such as epoxy resins may be added to improve the adhesion to the supporting substrate, and various anti-fogging methods may be used to prevent fogging. It is also effective to further add agents.

When using the photosensitive resin composition of the present invention, the above-mentioned thermal polymerization inhibitor, sensitizer, and filled polymer compound are mixed in an inert solvent such as an aliphatic alcohol, a ketone, an aromatic legated water, and an aromatic compound. - and then coated by a conventional method on a support on which an image of the corrosion-resistant layer is to be obtained, and dried to remove the solvent.

Of course, the photosensitive resin composition of the present invention is implicitly sufficiently stable that it can also be used in a method that does not involve the use of a solvent in the mixture-activation with a heated roller. The film obtained as a photosensitive resin film on a support is exposed to active light through a mask in the usual manner, and when exposed to the mask, a sharp negative image is obtained. Can be used as a *gland resistant material for plating.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto. Example 1 Nitrogen introduction tube, lower opening), IIF needle, cooling tube.

In a 500 red round bottom flask equipped with a stirrer, 200Kt of dry toluene, 0.8F paramethoxyphenol, 2-
Take methyl-1,5-propylene glycol 10F,
A dry toluene solution of [2,4-)luene diincyanate 5O8Of was stirred in SaC for 1 hour and added dropwise at 2 hours, and further reacted at 80C for sO. Then, 2-hydroxyethyl methacrylate 251 was converted to SaC
After stirring and vortexing the mixture for 1 hour, 0.52% of triethylenediamine was added, and the mixture was allowed to react at 80C for 1 hour. Next, add 10 liters of methanol and let it stand for 1 hour.
, and then dried under reduced pressure to obtain a white solid reaction product.

The above reaction product 2.75f and polymethyl methacrylate 2. Of, benzophenone 0.2F, hydroquinone 0. ! When Sf and Crystal Violet 01t were dissolved in 20fK of Trichloride and vigorously stirred for about 10 minutes using a homogenizer, the pigments were finely dispersed. The thus-obtained soybean paste was coated on a PICT film (75 parts) using a mare bar coater and rolled at 40 t' for 5 minutes to obtain a blue sheet. The thickness of the m fabric layer is approximately 5
It was μm. Next, the photosensitive film obtained by pressing in this way is mixed with a transparent photographic negative. ! It was heated for about 10 minutes after removing the 40a*O bag from the light source using an Oakjet printer (Oak operating system, 2Kw mercury lamp). Immediately after fogging, the light irradiated area turned yellow and L+'lIlLun could be identified as a circle. Next, when a mixture of 10 parts of chlorocene and 90 parts of r)-hexane was used, the compound in the uncut part was removed from the PET film, and the photocured part became insoluble.
remained on the PET film. The thus obtained 91Ikl had extremely good writing and adhesion properties on PET substrates.

Sou-Example 2 5+! crow? Reaction product 52 obtained in I11, polymethyl methacrylate-methacrylic class copolymer (9515
Weight ratio)2. Of, Mihi'i-ketone 0.2 f1 Hydroquinone 01f, and Crystal Violet 001f were dissolved in Toluene/19v in the same manner as in Example 1 to obtain a photosensitive resin composition. It was applied to a stretched laminate and dried at 60C for 5 minutes.The thickness was 20μ.

Next, light was applied through the mask for about 60 seconds using an Oak Jet Glinter (manufactured by Oak! 9', 2Kw water lamp) from a distance of 40~ from Kuga. Next, he was killed using Chlororyu. The corrosion-resistant coating obtained by this method is sufficient for copper etching using chloride-free double-ridges, and can also be used for various types of plating. A good 1-lint circuit was obtained in the O.L. system amendment (spontaneous) April 1981 181j 'llI Director-General of the Agency Kazuo Sugi 1 Indication of Case Patent Application No. 1988-67888 2 Invention Name Photosensitive Resin Composition 3 Relationship with the Groove for Correction Patent Applicant (290) Gwisel Chemical Industry Co., Ltd. 4 Agent is 30-200, preferably 50-1501
It is appropriate to use E parts. ” is inserted.

(+) rf/Il Page 1, line 4, “bensyl” was corrected to “hendiine methyl ether”

Claims (1)

[Claims] A monomer containing an incyanate group obtained by reacting 2-methyl-1,3-propylene glycol with a diincyanate compound or a low polymer thereof is further added to glycol monoacrylate or glycol monomethacrylate. Photosensitive resin composition containing as an active ingredient a mixture of 91 or 29 or more unsaturated monomers or unsaturated low polymers obtained by reacting with