JPS6091352A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. which can be thoroughly cured by short time of heating and is suitable for forming a permanent protective film by combining a polymer having an epoxy group and an amine imide. CONSTITUTION:A resin compsn. is formed of (a) an unstad. compd. which has substantially at least two ethylene groups at the terminal and is photopolymerizable, (b) a photopolymn. sensitizer, (c) a linear high polymer compd. having an epoxy group at the side chain and (d) the amine imide expressed by the formula I (R1, R4 in the formula are the aliphat. hydrocarbon having 0-6 carbon atoms that can contain oxygen atoms, R2, R3 are the aliphat. hydrocarbon having 0-6 carbon atoms). The resin is photopolymerized with the (a) and (b). The (c) functions as a high polymer for forming a film in the compsn. and acts further synergistically with the (d) to increase the mol.wt. of the resin and to crosslink the same in extremely short time at 150 deg.C thereby rendering mechanical strength and heat resistance to the resin.

Description

[Detailed Description of the Invention] The wooden material is photopolymerizable! The present invention relates to a photosensitive resin composition for forming an i-image.

Conventionally, a resin composition made of a polymeric material, a photopolymerizable monomer, a photopolymerizable sensitizer, etc. is coated or coated on a substrate, and then exposed to active light such as ultraviolet light through a negative image or the like. It is known that the above IV image can be expressed on a substrate by irradiating it with light and polymerizing the areas that are exposed to the light; by crosslinking and making the areas insoluble in the solvent and eluting the areas that are not exposed to the light. The printing plate phase and pudding 1 are
Used in the manufacture of wiring boards, however, with the above composition #:t f! 7 pictures $1
11. Coating t' solvent resistance, chemical resistance, heat resistance +1 and P mechanical strength are insufficient and use as a protective membrane)11. Concave T
:I limited.

For example, these coatings can be prepared using neutral, weakly acidic acid solution 11r.
), 1 is resistant to strong acids and alkaline solutions.
Therefore, the filling solution for etching, plating, etc.
types are limited. In addition, organic solvents such as toluene, trichlene, and methyl ethylgtone are weak in KVi and have insufficient heat resistance and mechanical strength, so they cannot be used as a permanent protective coating.

For the purpose of forming a permanent protective coating, systems containing epoxy compounds and their curing agents have been proposed, but these have a short pot life at room temperature, require high temperatures and long periods of time to cure, and may warp the substrate. or cause corrosion of metal chips.

Also, Special Publication No. 52-430929, Special Publication No. 52-43
In Publication No. 091, Special Publication No. 56-3539, etc.,
In order to form a permanent protective film, attempts have been made to include an acid component in the copolymer binder to accelerate curing, but #i curing is insufficient under normal conditions, and the soldering heat resistance and It is weak in solvent resistance and alkali resistance, and furthermore, its cold and heat cycling properties are not sufficient.

Kibatsu 11 solves the above-mentioned conventional drawbacks, and provides a photosensitive resin composition that has excellent storage stability, can be sufficiently cured by heating for a short time, and is suitable for forming a permanent protective film. The purpose is to

Kihatsu! The gist of 1 is as follows: (al: a photopolymerizable unsaturated compound having substantially at least two terminal ethylene groups; (bl: a photopolymerizable sensitizer; (cl: a linear polymer compound having an epoxy group in its side chain; dl Amine imide represented by the following general formula, 0 0H (R1, R4 are aliphatic p-hydrogen 3!(, R2+ R3 has 0 to 6 carbon atoms) A photosensitive resin composition comprising aliphatic hydrocarbon atoms).

Kihatsu EJi Unsaturated compounds in VC (at t:f,
It has substantially at least two terminal ethylene groups. Substantially at least two, there may be compounds with only one terminal ethylene group in the system, compounds with three or more terminal ethylene groups, and overall compounds with one terminal ethylene group on average. This means that there are at least two of them.

As unsaturated compounds (at), acrylic esters or methacrylic esters of polyhydric alcohols are most suitable, and specific examples include triethylene glycol, tetraethylene glycol, ethylene glycol, propylene glycol, trimethylol promonomer, Examples include acrylic acid or methacrylic esters such as pentaglythritol and neopendel glycol.The amount of this component used in the photosensitive resin composition is 10 to 90% by weight, preferably 15 to 60% by weight. It is.

A sensitizer (bl) is a sensitizer that initiates the polymerization of unsaturated compounds when irradiated with actinic light, and in some cases increases the action of the main sensitizer and the main sensitizer. A combination of secondary sensitizers may be used.

The sensitizer (bl) may be a conventionally used sensitizer, but phenylketone-based sensitizers are preferred, and specific examples include KVi benzophenone, P, P-bis(dimethylamino) Benzophenone, P-aminobuenyl ketone (hereinafter referred to as Michler's ketone), benzin, benzin methyl ether, benzoin ethyl ether, benzin methyl ether, penzoin isoglobyl ether, benzyl anthraquinone, 2-methyl-
Anthraquinone, 2-ethyl anthraquinone, 2-t
-butyl-anthraquinone, 1 t/ton, 2-aminoanthraquinone.

The above-mentioned sensitizer tb+ performs the same function, and by adjusting the active light absorption range different from that of the sensitizer tb+, it can change the C1 polymerization initiation efficiency and further shorten the exposure time. Particularly suitable is a mixture of benzophenone and mitragtone. The amount of this component used is 0.01 to 15% by weight in the photosensitive resin composition, and
It is 1 to 10% by weight.

Next, the linear polymer compound (cl
Fi, fl! l It has an epoxy group in the base,
For example, by homopolymerizing or copolymerizing an epoxy group-containing acrylic yarn monomer such as glycidyl methacrylate or glycidyl acrylate with a vinyl monomer, leakage can easily occur.

Linear polymer compounds (specific examples of cl include methyl methacrylate-glycidyl methacrylate copolymer, methyl methacrylate-glycidyl methacrylate 1/-to-acrylonitrile copolymer, edyl acrylate-glycidyl acrylate styrene copolymer) Copolymerization, pendyl meccrylate-glycidyl meccrylate-styrene copolymer, etc. are obtained.A linear Is molecule compound (in Cl, epoxy group-containing 1
The single claw body should preferably account for 1 to 70% by weight, preferably 5 to 40% by weight. The amount of the linear polymer compound [cl] in the photosensitive polymer composition is 10 to 90% by weight, preferably 30 to 70% by weight.

Water component, linear polymer compound (cl #'i, functions as a film-forming polymer in the composition, and is removed after 31!
It is characterized in that it reacts synergistically with amine imide of about 12.150"C' and is capable of high molecular weight and crosslinking in a very short time. Therefore, the weight average high molecular weight is 10,000 to 500,000, making it a good choice. Chills between 100,000 and 300,000.If the molecular weight is too low, it will take a long time to cure.If the molecular weight exceeds 500,000, the curing will be too fast and the temperature will be too low to control, requiring extreme care in handling. It becomes like this.

One of the features of the present invention is that the linear polymer compound (CLK) has better film-forming properties and can be cured in a short period of time at about 150°C, without causing warping or corrosion on precision substrates, etc. It is possible to form a protective film with sufficient mechanical strength and heat resistance, and furthermore, it has a sufficiently long pot life as a photosensitive polymer composition.

One of the constituent components of the photosensitive resin m-acid of the present invention is amine imide (dl) represented by the following general formula.

O0H (R1, R4 #″i 0 to 6 that can contain oxygen atoms
(R2+ R3 is an aliphatic hydrocarbon having 0 to 6 carbon atoms) Conventionally, in a photosensitive plum fat composition using an epoxy compound, it has been used as a latent hardening agent for the epoxy compound. Examples include monoedulamine trifluoride, boron trifluoride benzylamine complex, sulfate tetrafluoride, adipic acid, dihydrazide, triethylaminoborane, phenylenediamine-zinc bromide complex, and dicyandiamide. The usage time is so long that it is impossible to save it.

I', P'-diaminodiphenylmethane, P, P'-diaminodiphenylsulfonic acid, 2-ethyl 4-ethylimidazole, etc. have also been found as latent curing agents with a long pot life at room temperature, but they require high temperatures and long periods of time for curing. This is undesirable because it may cause the substrate to warp or prolong the processing time.

In addition, the conventional latent curing agent mentioned above diffuses into the IJ and fully curved surface of the substrate, which has a negative effect on precision electrical circuits, and is used in the production of printed wiring boards. was not suitable.

As a result of intensive research, Raikori I'f discovered that the amine imide (di fi) of the general formula (I) has a sufficiently long pot life at room temperature as a phosphorescent abrasive composition, and has an appropriate level of ?, A degree, and short If it cures in a long time and forms a permanent protective coating, excellent solvent resistance +1, alkali resistance +1, and solder heat resistance can be obtained.

Amine imide of the above general formula (I) (di is R1-R4
If too much aliphatic hydrocarbon is present or aromatic groups are included, sufficient heat resistance etc. will not be obtained.

Preferably, R2 and R3 are a methyl group or a nitro group, and up to a hexyl group is practical. R1 and R4 also have carbon number #-i
It is preferably 6 or less, and may contain an oxygen atom in the form of an ether bond. The most suitable bond for R1 and R4 is the case where the carbon-m element has a double ^17 bond.

These reasons are not due to 111FI termination, but it is believed that the amine imide (di) of the general formula (I) has appropriate polarity to be uniformly dispersed in the photosensitive resin composition and will not lead to adverse effects on the substrate surface. It will be done.

In addition, when J + R4 contains a double bond, it is incorporated into the polymerization system by actinic light irradiation, improving dispersibility and linear polymer compound (cl
It is presumed that Yoshikage Satoshi appears in the hardening of.

Moreover, the amine imide (di V′i, 1
Rapid KM-like polymer compound (Cl-I) can be cured in a short time of 10 to 30 minutes at about 50℃, and sagging alkali resistance can be obtained, and solvent resistance and soldering heat resistance can be obtained. Direction 1-shi,
In addition, the lightness of the cold and heat green coating also provides an excellent protective coating for the gun.

Aminimide fdl is preferably used in an amount of 02 to 12% by weight in the 111f% photosensitive fat composition.

In addition to the above-mentioned essential components of the unreleased photosensitive resin composition 1, it is possible to further contain secondary components for various purposes.

That is, thermal polymerization inhibitors for improving storage stability, plasticizers for improving coating properties, adhesion improvers, dyes 1, pigments, and other fillers.

1. The photosensitive resin composition of the present invention has photosensitivity similar to ordinary photosensitive resins, and undergoes photopolymerization by irradiation with actinic light.
Furthermore, it is sufficiently stable in Vi thermal terms at temperatures below 80°C, and a permanent protective film can be formed by conventional methods.

That is, through the photosensitive resin composition of unreleased FJ1? tt t:
j. Adjust the solution by dissolving it in an organic solvent such as methyl ethyl ketone, toluene, methyl cellosolve, or chloroform to a concentration of 3 to 60% by weight, and protect it using the method (1) or (2) below. A photosensitive layer is formed on the substrate to be treated.

(1) Apply a solution containing the photosensitive resin composition to the substrate-1- and dry it.

(2) [8] Boil the liquid in which the light citrus composition was dissolved.
Apply to the film of Chilentele 7 crate tube and dry.

The obtained filter is attached to a substrate using a hot roll. In this case, it is also possible to stack the photosensitive N & ζ storage films of the film to maintain γf-.

Violet (purple) is applied to the substrate on which the photosensitive layer is formed through a negative mask.
The FPA is irradiated with active light, and the exposed areas are photopolymerized and cured by crosslinking. Next, the unexposed areas are eluted and developed using 1,1,1-)lichloroethane or the like. In this way, the obtained image-like protective film becomes a corrosion-resistant film for ordinary surface modification processing such as etching and plating.
In addition, heat curing for a short period of time at around 150°C within 1 hour provides excellent heat resistance and 1 (excellent mechanical strength) resistance to corrosion by halogenated R-hydrogen solvents such as ice cream solvents and methylene dichloride. It also withstands strong acid and alkaline aqueous solutions. Therefore, it can be used as a permanent protective coating for soldering heat resistant VCfFE resists and the like. In addition, prior to heat curing, post-exposure to ultraviolet rays or the like at an intensity of 1 to 3 Jlcrl (by doing so, it is also possible to form a protective film having a lower strength).

It can also be used as photosensitive paint, plus deck relief, printing Fj, H material.

Examples of the present invention will be described below.

40) (Mw-210,000) C! A dacrylate copolymer pig
40 parts pentaerythriol triacrylate 30 parts Benzophenone 3 parts Michler's ketone 05 parts P-methoxyphenol 0.5 parts Amine imide (compound 4') 1 part Medyl edyl ketone 2() 0 parts 0H Table 1 Above The photosensitive resin composition was adjusted to 1VllJ with the formulation #1
IO+) at room temperature and 1 at 80'C.
The photosensitive layer was dried for 0 minutes and had a thickness of 5 G//m.

Next, the Kfx light layer was covered with a transparent polyethylene terephthalate film having a thickness of 25 μm, and was irradiated with ultraviolet rays of 100 mJ/lyl from a Shode mercury lamp through a negative mask. Peel off the polyethylene terephthalate film, 1.
1.1-Trichloroethane was sprayed in the direction for 90 seconds to elute the unexposed areas and development was performed. Next, heat treatment was performed at 150°C for 10 minutes (for Example 2.3 VC, 150°C
After heating for 5 minutes at 50° C., a protective film with a precise image corresponding to a negative mask was obtained.

This protective coating consists of methyl ethyl ketone, acetone, chloroform, trichlene, methanol, 50% sulfuric acid aqueous solution,
There was no change when immersed in toluene and xylene for 1 day, and even when immersed in a sodium hydroxide solution of P II 12 at 70°C for 1 day, no abnormalities were observed. There wasn't.

Further, there was no change even after repeated cooling and heating at -65°C and 125°C at 60 minute intervals, and further immersion in a simmering bath at 260-270°C for 2 hours. From the above, it has been found that the obtained protective coating # can be satisfactorily used as a resist for etching, plating, strong alkaline mm plating, and as a solder resist that requires soldering heat resistance.

<Example 4> Benzyl meccrylate/glycidyl methacrylate/styrene copolymer (60:30:io) (Rlw - 200,000) 60 parts Pentaerythritol triacrylate 30 parts Pentuin isofuroyl ether 5 parts P-methoxyphenol 0 .5 parts amine imide (compounds shown in Table 1) 2 parts methyl ethyl ketone 100 parts The photosensitive resin composition obtained with the above formulation was coated on a 25 μm thick polyester ethylene terephthalate and dried for 17.5 minutes.
A photosensitive layer having a thickness of pm was formed. Cleaned. The copper plates were laminated under pressure using a hot roll.

Then, exposure and development were carried out according to the force method of Example 10,
The same heat treatment was performed at 150° C. for 5 minutes, and the same results as in Example 1 were obtained. Also, polyethylene terephthalate film tut! Cloth N dried 6-layer light W1 at 40℃ 6
Even after storage for several months, there was no problem with the VC used.

<Comparative Example 1, λ> When the amine imide in Example IK was replaced with that in Table 1 and the same test (heat curing at 150°C for 30 minutes) was conducted,
When immersed in methyl ethyl ketone, acetone, or chloroform, the resistance was only within one hour, and even after repeated cooling and heating, peeling and cracking were observed between the substrate and the substrate after 5 cycles.

Comparative Example 3 1-dicyandiamide was used in place of the amine imide in Example IK. However, the obtained photosensitive resin composition was
It was only usable for one day at 0℃. In addition, those exposed and developed at 150°C for 30 minutes and cured by heating are 260°C.
The coating melted in 30 seconds during one round of heating, and cracks occurred after 5 cycles of repeated cooling and heating. Then 170
C. for 3 hours, the heat resistance improved, but the substrate warped due to high temperatures, and hardening took a long time, making manufacturing complicated.

As mentioned above, the 171g photosensitive rhubarb composition has excellent storage stability, the reaction progresses satisfactorily in a short time at a relatively low temperature during curing, and it is resistant to solvents, alkalis, and heat. A protective film with good properties can be formed.

6゛W “Ex-Fi person” Sekisui Chemical Co., Ltd. Representative Mototoshi Tora Numa

Claims (1)

[Scope of Claims] 1(a) A photopolymerizable unsaturated compound having at least two substantial terminal ethylene groups, (bl photopolymerization enhancer, (cl having an epoxy group in the side chain) linear polymer compound,
(dl Aminimide expressed by the following general formula °, 0 01
1 (R,,R4)Aliphatic hydrocarbon having 0 to 6 #1 elementary atoms which may contain 1 acid atom, R2+ R3
1. A photosensitive resin composition characterized in that the main component is an aliphatic hydrocarbon having 6 to 6 carbon atoms. 2 The amine imide is represented by the general formula (1), where the aliphatic hydrocarbons R1 and R4 are carbon-P,! 2. The sensitive resin composition according to item 1, which has an elementary double bond.