DE3215513A1 - Photosensitive resin compsn. - Google Patents

Abstract

Photo-sensitive resin compsn. contains (A) a polymer imparting film-forming properties to the resin compsn. and prepd. by using, as co-monomer, a monomer contg. an aliphatic amino gp. and having formula CH2:CR1-CO-(OCH2CHR2-)n -OCH2CHR3NR4R5 (where R1, R2 and R3 each is H or Me ; R4 and R5 each is 1-4C alkyl or R4 and R5 together with the N atom form a satd. alicyclic 4 to 7-membered ring, and n is O or integer 1-3), (B) an ethylenically unsatd. cpd., (C) a photo-sensitiser and/or photo-sensitiser system generating free radicals by actinic light, and (D) an organic halogen cpd.. A photo-sensitive element is claimed comprising a carrier film coated with a layer of the photo-sensitive copmpsn. The compsns. can be used as etching- and plating covers in the prodn. of printed circuit boards and metal precision working pieces. Combined (A) and (D) presence improve adhesion to substrate. The compsns. have high photo-sensitivity and resistance to plating.

Description

Description

The invention relates to a photosensitive resin composition.

It particularly relates to a photosensitive resin composition for manufacture of etching resist and plating resist with very good adhesion and high Sensitivity that occurs in the manufacture of printed circuit boards, metal precision workpieces and the like can be used.

In the field of printed circuit board manufacture, metal precision workpieces and the like are known, photosensitive resin compositions and photosensitive Elements made using the photosensitive resin compositions, as covering materials in the modification of substrates using chemical and electrochemical processes such as etching, plating and the like. As the photosensitive members, those obtained by a layer of a photosensitive resin composition is laminated on a support layer. These photosensitive resin compositions and photosensitive members that are obtained when using these resin compositions, they must have good chemical resistance and have good adhesion to the substrate, so that - if they are used as Etch resist or plating resist are used - endure this and they must also have sufficient photosensitivity for practical use own.

In the field of printed circuit board manufacture, circuits developed with higher density. The photosensitive resin compositions and photosensitive Elements that are used for this must have better adhesion to the Have substrate than the previous ones. With a view to shortening the process should the photosensitive resin masses and the photosensitive Elements have a higher photosensitivity.

A general method for making a photosensitive Resin composition with higher photosensitivity, especially in the polymerizable System, which unsaturated compounds and initiators that form free radicals, contains, consists in the photosensitivity of the unsaturated compounds to increase.

Various unsaturated compounds have been studied for this purpose. In general, polyacrylates of polyhydric alcohols are widely used. Among them are the polyether bonded acrylates, especially those that have the Have structure of polyethylene glycol, effective as highly sensitive acrylates. Examples of such acrylates are tetraethylene glycol diacrylate, nonaethylene glycol diacrylate etc. which are commercially available, e.g., NK Ester A-4G, A-9G from Shin-Nakamura Kagaku K.K., Japan, in some cases a polyethylene glycol structure introduced into other components besides the unsaturated compounds to the same Purpose to achieve. The use of such compounds for this purpose is exemplified described in JA-PS 33801/80.

Such compounds as acrylates with a polyethylene glycol structure, are for increasing the sensitivity of a photosensitive resin composition or of a photosensitive member using the resin composition is effective. However, they have the disadvantage that the plating resistance a covering compound produced therefrom is undesirably deteriorated. Therefore, the usable amount of such compounds as the acrylates with a Polyethylene glycol structure, limited if plating resistance is required is, and thus the sensitivity is deteriorated depending on the decreased one Amount of acrylates.

In order to avoid such a disadvantage, the use of a Agent that improves adhesion, such as 1,2,3-benzotriazole, in JA-OS 9177/75 suggested.

The effect of such an agent, which improves adhesion, is explained as saying that the agent for improving the adhesion in the resin composition is oriented towards the substrate as well as the copper surface and in direct Contact with the on the surface of the substrate according to a method known per se applied or laminated mass and that they are a single when foaming Molecular layer that forms the adhesion between the substrate and the resin composition or the cured product. The effect of such a means of improvement the adhesion is effective in some cases, but a poor one is sometimes obtained Influence on later processes, since on the surface of the substrate by the means that improves the adhesion, a stiff film is formed. For example, kick with benzotriazole there are disadvantages, since a photosensitive layer forms the substrate surface discolored noticeably with the lapse of time, and when the photosensitive layer of the unexposed surfaces by a technique such as development or the like Process is removed, the substrate surface shows an etch resistance or less plating metal is deposited. As mentioned above, so occur some difficulties in using an agent to improve adhesion on.

The present application is based on the object of a photosensitive To provide resin mass available, which do not die. Disadvantages of the known resin masses owns.

The invention is a photosensitive resin composition which has sufficient adhesion and plating resistance without a Means to improve adhesion must be used.

The invention relates to a photosensitive resin composition which (a) a polymer with film-forming properties, which is formed using a monomer as a comonomer which has an aliphatic amino group represented by the formula: contains, wherein Rn, R2 and R3 are independently hydrogen or a methyl group, R4 and R5 are independently an alkyl group having 1 to 4 carbon atoms or where R4 and R5 together with the nitrogen atom are a saturated alicyclic 4- to 7-membered Form ring and n is 0 or an integer from 1 to 3, has been obtained, (b) an ethylenically unsaturated compound, (c) a photosensitizer and / or a photosensitizer system, which form free radicals through actinic radiation, and (d) contains an organic halogen compound.

It is a feature of the present invention that a monomer of Formula (1) for the formation of the polymer (a) and an organic halogen compound (d) used as essential components.

The polymer (a), which gives the resin composition film-forming properties, can be easily using according to per se known vinyl polymerization methods as comonomers of at least one monomer containing aliphatic amino groups of formula (1) and one or more other polymerizable vinyl monomers getting produced.

Examples of other polymerizable vinyl monomers are methyl methacrylate, Butyl methacrylate, lauryl methacrylate, ethyl acrylate, methyl acrylate, styrene, vinyl toluene, α-methylstyrene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, etc.

As aliphatic amino groups-containing monomers of the formula (1) those with a basic amine structure are more preferred than those with a nucleophilic Amine structure. This is because the aliphatic amino groups that are in the side chains of the polymer (a) are introduced, form quaternary ammonium salts in bulk supposed to be by directing the protons produced by irradiation with actinic Light generated, bind.- Therefore, aliphatic alkylamines are more suitable steric hindrance preferred. Taking these things into account, R4 and R, in the formula (1), independently of one another, preferably a methyl group, a Ethyl group, a propyl group, an isopropyl group, an n-butyl group or a Isobutyl group or R4 and R5 together with the nitrogen atom form a saturated one alicyclic ring such as a piperidine ring, etc. More preferred examples of R4 and R5 in the formula (1) are independently a methyl group and an ethyl group.

The length of the alkylene group in the aliphatic amino group containing Monomers of the formula (1) can be selected depending on the purpose. A longer one Alkylene group length gives better photosensitivity. on the other hand the presence of such an alkylene / ether bond increases the resistance against plating as in the case of the polyethylene glycol structure.

With these considerations in mind, there is a longer alkylene group not required and * 'nt' in the formula (1) preferably means 0 or a whole Number from 1 to 3.

Dialkylaminoethyl acrylates and dialkylaminoethyl methacrylates are in particular preferred. Particularly preferred examples of the monomers of the formula (1) which are easily are commercially available are N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate and similar compounds.

The content of the aliphatic amino group-containing monomer in the polymer (a). preferably 0.1 to 10% by weight, more preferably 0.2 to 5 wt., -, It is very surprising> that one even when the content of the Monomers represented by the formula (1) is 1% by weight or less, a sufficient effect receives.

The organic halogen compounds (d) used are preferably those which easily release halogen radicals by means of actinic light or which easily Release halogen radicals through chain transfer. Among these are aliphatic Halogen compounds with rather weak carbon / halogen bonding power, in particular aliphatic halogen compounds with two or more halogen atoms attached to one Carbon atom are bonded, and organic bromine compounds are preferred.

Examples of organic halogen compounds (d) are carbon tetrachloride, Chloroform, bromoform, iodoform, methylene chloride, 1,1,1 -trichloroethane, methylene bromide, Methylene iodide, carbon tetrabromide, 1,1,2,2-tetrabromoethane, pentabromoethane, tribromoacetophenone, Bis- (tribromo- methyl) sulfone, tribromomethylphenyl sulfone, vinyl chloride, chlorinated olefins and the like. These organic halogen compounds can alone or used as their mixtures. Among the organic halogen compounds (d) those having a tribromomethyl group give the particularly preferable effects.

The amount of organic halogen compounds is not particularly limited, but preferred are 0.2 to 10 moles, more preferably 0.5 to 3 moles per mole of aliphatic Amino group-containing monomers of the formula (1) are used.

In the present invention, all reactions in the photosensitive resin composition are not clearly known, but the following reactions seem to take place: that is, halogen radicals formed directly or indirectly from the organic halogen compound by irradiating with actinic light generate hydrogen halides by removing hydrogen a hydrogen donor and the hydrogen halides react with the alkylamino groups in the side chains of the polymer (a) to form quaternary ammonium salts. This can be represented by the following equations: RX hv, R + X. Hydrogen donor Hydrogen Donor HX Polar groups having an ionic structure are newly introduced into the side chains of the polymer (a) by irradiation with actinic light, which apparently improves the adhesion in the present invention.

Generally speaking, it is caused by the presence of polar groups in the side chains of the polymer (a) physical adhesion to the substrate and the cured material, however, it does not always show such an effect a common acidic or alkaline etching solution and a plating solution. this is particularly noticeable in the case of performing plating. For example if the polymer (a) with carboxyl groups in the side chains is sufficient Resistance to the acidic etching solution, but a significantly reduced one Resistance to the alkaline copper pyrophosphate plating bath. These Inclination is particular in the above-mentioned system, which is polyethylene glycol acrylates contains, pronounced. In such a system, the absorption of the hardened material of saturated water in water proportional to the content the polar groups and the content of the polyethylene glycol acrylate derivatives increased, which is the main cause of the deterioration in plating resistance is. Although it is believed that polar groups, especially groups with ionic Structure in which the hardened material differs from the photosensitive resin composition and contains the polymer (a) and the organic halogen compounds (d), and in the photosensitive member obtained by using this resin composition is produced, it is very surprising that according to the invention plating resistance is improved.

It is also very surprising in the present invention that the photosensitivity of the photoemp- sensitive resin mass is improved. It also follows that the present invention is very useful is.

As the ethylenically unsaturated compound (b), there can be known ones Use compounds alone or their mixtures. Because of the high photo sensitivity the use of acrylate monomers or methacrylate monomers is preferred. Particularly preferred examples of acrylate monomers or methacrylate monomers are polyacrylates or polymethacrylates of polyhydric alcohols, such as trimethylolpropane triacrylate, Pentaerythritol triacrylate, 1,6-hexanediol diacrylate, 2,2-bis-C4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxyethoxyphenyl) propane, dipentaerythritol pentacrylate, trimethylolpropane trimethacrylate etc., acrylic acid or methacrylic acid adducts of trimethylolpropane triglycidyl ether, Epoxy acrylates or methacrylates, such as acrylic acid or methacrylic acid adducts from Bisphenol-A-epichlorohydrine epoxy resins, unsaturated polyesters with low molecular weight, like the condensates of phthalic anhydride / neopentyl glycol / acrylic acid (1: 2: 2 molar ratio) etc. Further preferred are compounds of the polyethylene glycol acrylate type or methacrylate types, such as diethylene glycol diacrylate, tetraethylene glycol diacrylate, nonethylene glycol diacrylate, Tetraethylene glycol dimethacrylate, polyethylene glycol (molecular weight about 400) diacrylate etc. used. The amount of these compounds should be determined within a range so that the plating resistance is maintained. The common use that with the above-mentioned polyhydric alcohol polyacrylates is particularly preferred.

As a photosensitizer or photosensitizer system (c), which Compounds known per se can form free radicals through actinic light use alone or as their mixtures.

Examples of photosensitizers are benzophenone and its derivatives, such as benzophenone, p, p-dimethylaminobenzo phenone, p, p-diethylaminobenzophenone, p, p-dichlorobenzophenone etc. and their mixtures, anthraquinones, such as 2-ethylanthraquinone, t-butyl anthraquinone etc., 2-chlorothioxanthone, benzoin isopropyl ether, benzoin ethyl ether, Benzyl, 2,4,5-triarylimidazole dimers etc.

The term flphotosensitizer system II is used in the present Registration used to be a combination of photosensitizer and sensitizing aid to describe. Examples of such photosensitizer systems are mixtures of 2,4,5-triarylimidazole dimers and 2-mercaptobenzoquinazole, leuco crystal violet, tris- (4-diethylamino-2-methylphenyl ) -methane and the like. It is possible to use such types of additives, although they do not have photoinitiating properties per se, they can a photosensitizer system with even better photoinitiation properties than Whole when used together with the above mentioned materials. Typical examples of such additives are tertiary amines, such as triethanolamine, when used with benzophenone.

In the photosensitive resin compositions according to the invention, the polymer is (a) preferably used in an amount of 30 to 80 parts by weight. The ethylenic unsaturated compound (b) is preferably used in an amount of 70 to 20 parts by weight is used and the total amount is 100 parts by weight. To 100 parts by weight of the Components (a) and (b) are preferably added from 0.5 to 10 parts by weight of the photosensitizer and / or the photosensitizer system (c), which free radicals by actinic May generate light, and 0.2 to 10 parts by weight of the organic halogen compound (d) to form the photosensitive resin composition. Regarding the order mixing components (a), (b), There are none (c) and (d) particular restrictions and any mixing method can be used.

The photosensitive resin composition of the present invention may further comprise one or several per se known dyes, plasticizers, pigments, means for increasing the fire resistance, stabilizers and the like, if necessary, as well as agents to improve adhesion.

The following examples illustrate the invention. All parts and percentages are expressed by weight unless otherwise specified.

Example 1 (I) Any polymer which has film-forming properties and contains an aliphatic amino group (hereinafter referred to as "polymer" is made by the following procedure.

Table I Monomer Mixture No. M-1 M-2 M-3 M-4 methyl methacrylate 98 96 97 97.5 ethyl acrylate 2 2 2 2 dimethylaminoethyl methacrylate - - 1 0.5 methacrylic acid - 2 - - Footnote: The total weight is 400 g in each case.

In a 1 liter flask are placed 250 grams of toluene and 150 grams of each Monomer mixtures M-1 to M-4 each 400 g, as listed in Table I, and heated to 850C while introducing a stream of nitrogen. Then will a solvent mixture containing 250 g of remaining ches Monomeres, 150 g of toluene and 0.56 g of azobisisobutyronitrile, drop by drop in the flask Added over 3 hours while the temperature is maintained at 850C. After completion After the addition, the flask is kept at this temperature for 4 hours. Then it will be a solution obtained by adding 0.28 g of azobisisobutyronitrile in 75 g of toluene dissolved, added to the flask dropwise over 30 minutes. After completion After the addition, the temperature is kept at this value for 4 hours. The reaction solution is then diluted with 75 g of toluene and 75 g of methyl ethyl ketone. You get the respective Polymer solution P-1 to P-4 with a non-volatile blindness content of 36 up to 38%. The properties of the resulting polymer solutions are shown in the table II stated.

Table II Polymer solution No. P-1 P-2 P-3 P-4 content of not volatile 36.2 37> 5 37.7 38.2 solids 1 (%) 36.2 57.5 37.7 38.2 Gardner viscosity (250C) Z1 Z2 Z2 Z3 + Z3 Z4 reduced viscosity 2.

Rsp | c 0.33 0.31 0.33 0.34 Comments on Table II: * 1: The values after drying at 108 ° C. for 3 h.

* 2: Using a Cannon-Fenske type capillary viscometer (Viscometer No. 25, C - 00301), a sample is prepared by adding 0.25 g of polymer Dissolve (on a dry basis) in 100 ml of methyl ethyl ketone and measure at 300C.

When the polymer solutions P-1 to P-4 are used, photosensitive Resin Compounds V-1 through V-6 as shown in Table III prepared.

Table III Mass No. (in parts) V-1 V-2 V-3 V-4 V-5 V-6 P-1 165.7 - - - 165.7 - P-2 - 157.1 - - - - P-3 - - 160.0 - - 160.0 P-4 - - - 159.2 - - Trimethylolpropane triacrylate 25 25 25 25 25 25 Tetraethyl glycol diacrylate 15 15 15 15 15 15 Benzophenone 4.5 4.5 4.5 4.5 4.5 4.5 Michler's ketone 0.5 0.5 0.5 0.5 0.5 0.5 Methylene-bis- (1,1-di-t-butyl- 0.5 0.5 0.5 0.5 0.5 0.5 4,4'-dimethylphenol) Carbon tetrabromide 2.5 2.5 2.5 2.5 - - Victoria pure blue 0.08 0.08 0.08 0.08 0.08 0.08 Leuco crystal violet 0.5 0.5 0.5 0.5 0.5 0.5 Methyl ethyl ketone 40 40 40 40 40 40 Each of the photosensitive resin compositions (varnishes) thus prepared (Vl to V-6) is uniformly coated on a poly (ethylene terephthalate) film with a thickness of 25 μm, so that a coated film with a thickness of 25 μm is obtained ym after drying. After drying at 80 ° C. for 5 minutes, the respective photosensitive elements as listed in Table IV (F-1 to F-6) are obtained. In Table IV, F-3 and F-4 are inventive examples and the other comparative examples.

Table IV Element No. F-1 F-2 F-3 F-4 F-5 F-6 paint used (mass No.) V-1 V-2 V-3 V-4 V-5 V-6 Film thickness (µm) 25 25 25 25- 25 25 (III) The degree of Sensitivity of each of the photosensitive members F-1 bis thus prepared F-6 is evaluated as follows.

Each photosensitive element (F-1 through F-6) is on a copper surface a laminate covered with copper, which is first underlaid by polishing Has been cleaned using a nylon brush. A Hitach high temperature laminator is used and the temperature of the rubber roller is 1650C. The product made in this way the photosensitive element and the laminate laminated with copper become at Left to stand at room temperature for 30 minutes and then with ultraviolet light from a 2 KW ultra high pressure mercury lamp (HMW-2000, manufactured-by ORC Seisakusho, Ltd.) by a gray scale negative (level tray No. 2 (21 levels) manufactured by Eastman Kodak Co., Ltd.) exposed for 15 s. After exposure to light it will the element left to stand for more than 30 minutes and then the Poly (ethylene terephthalate) film is peeled off and then using developed from 1.1 trichloroethane.

The degree of sensitivity by the number of steps on the step tray, which were not washed out in the development is evaluated and in the following referred to as the ST stage number. The results are given in Table V.

Table V Item No. ST Stage Number * F-1 6.0 F-2 6.5 F-3 8.1 F-4 7.9 F-5 5.2 F-6 6.6 Note: *: The figure at the first decimal place of the ST level number means the value of the degree of swelling of the uppermost hardened material, in one evaluation of 10 levels.

From Table V it follows that the systems according to the invention, which both contain the polymer (a) as well as the organic halogen compound (d), i. e. F-3 and F-4, show high ST stage numbers, meaning that F-3 and F-4 are the highest Have a degree of sensitivity. This means, for example, that the time in s, which is required to expose them to achieve the same number of ST levels, F-3 and F-4 can be reduced in 30 to 60% of cases compared to F-1.

(IV) Using the same procedures as in (III) above has been described, a laminate of a photosensitive member and a with copper fer coated laminate with ultraviolet light through a Exposed negative with a given print pattern and developed so that the ST level number is 8 levels.

Then the developed element is coated with copper in a copper pyrophosphate plating bath plated and then a luster-free tooth plating takes place. The pre-treatments and plating conditions are given in Table VI.

Table VI Treatment stages Kupferplat- Newtraclean 68 (manufactured tational pretreated by Shipl'y Co.) 50 ° C for 2 min lung washing with water for 30 s aqueous solution of ammonium persulfate (250 g / l, RT) 1 min Wash with water for 30 s dil dil H2S04; (10%) 30 s Wash with water for 30 s Copper Pyro Bath Temperature (OC) 55 PlhatPthaerung current density (A / dm2) 3.2 Current passage time (min) 45 Tinplate washing with water for 1 min preparation treatment borofluoric acid (20% aqueous Solution) 2 min Gloss-free bath temperature (OC) 23 Tin plate current density (A / dm2)?, 68 tation Current passage time (min) 15 After plating, the surfaces are examined with the naked eye and rated as indicated in Table VII.

Table VII Element Element Only. r. P1attierw1gabewert Pl F-2 | 0 | F-4 | 0 F-5 F-6 Evaluation standards: no plating penetration.

The masking compound around the circuit is discolored.

The plating solution has penetrated a little.

Plating penetration takes place to some extent.

Plating penetration takes place to a great extent.

C omparison 1 A mass is produced as follows.

Ingredients Parts P-1 165.7 Trimethylolpropane Triacrylate 35 Tetraethylene Glycol Diacrylate 5 benzophenone 4.5 Michler's ketone 0.5 Methylenebis- (l, -di-t-bulyl-4, 41-dimethylphenol) 0.5 carbon tetrabromide 2.5 Victoria pure blue 0.08 leuco crystal violet 0.5 methyl ethyl ketone 40 In this Comparative Example 1, the amounts of trimethylolpropane triacrylate were and tetraethylene glycol diacrylate were changed, and particularly the proportion of the latter was changed substantially degraded.

Using the same procedures as described in Example 1, the ST grade number and plating rating were obtained as in Table VIII.

Table VIII Element No. ST Grade Number Plating Rating Fl 6.0 F-3 8.1 Comparative Example 1 4.2 It is clear from Table VIII that the plating properties can be improved if the amount of tetraethylene glycol diacrylate is decreased to a low level, but that the degree of sensitivity is conversely decreased.

Example 2 Polymers are prepared in the same way as described in Example 1 (.I) using the following monomers containing aliphatic amino groups: The compound (2) which can be obtained in the market is used as it is. The other compounds are synthesized by a known method using the corresponding alkylamino alcohols and methacrylic acid or acrylic acid. The compositions of the raw materials for the production of the polymers are as follows: Ingredients Parts Methyl methacrylate 96 Ethyl acrylate 2 Acrylamide 1 Monomers of the formula (2), (3), (4) or (5) 1 The polymers obtained have reduced viscosities (# sp / c) in the range from 0.30 to 0> 33. The following photosensitive resin compositions are produced using these polymers.

Components Parts of the polymer which contains the monomer units of (2), (3), (4) or (5) contains 60 pentaerythritol triacrylate 30 tetraethylene glycol diacrylate 10 benzophenone 4.5.

Michlert's ketone 0.5 methylenebis (1,1-di-t-butyl-4,4'-dimethylphenol) 0.6 carbon tetrabromide 1.5 pentabromoethane 0.5 leuco crystal violet 0.3 aizen spilon green 0.3 methyl ethyl ketone 40 Using the same procedure as in the example 1 (II), photosensitive members having a resin film thickness of 50 µm after drying on a poly (ethylene terephthalate) film. The resulting photosensitive elements are exposed to ultraviolet light during Exposure for 20 s and then development with 1,1,1-trichloroethane in the same manner as described in Example 1 (III).

The ST stage numbers are given in Table IX. For comparison, will a photosensitive element, which is obtained by using as polymer P-1, which has no aliphatic amino group, used, also tested (comparative example 2) and the results are also given in Table IX.

Table IX Element No. Containing Aliphatic Amino ST Groups f number of monomer in the polymer F-7 formula (2) 8.3 F-8 formula (3) 8.6 F-9 formula (4) 8.9 Formula (5) 8.3 Comparative Example 2 none 6.5 Example 3 The same procedures, as described in Example 1 (I) P-3 were repeated, except that the amount of azobisisobutyronitrile was changed to 0.42 g. One receives a Polymer P-5 with a reduced viscosity (tsp / c) of 0.39. Under use A photosensitive resin composition V-11 is prepared from P-5, the following specified components are used. For comparison, a polymer which obtained by using the same monomer mixture as in M-1 in Table I in the example 1 is used and the same synthesis method as described for P-5 is used, manufactured. It has a reduced viscosity tksp / c) of 0.40 (polymer P-6, Comparative Example 3).

Components V-1 1 Comparative example (parts) game 3 (parts) P-5 50 (dry basis) P-6 - 50 (dry basis) pentaerythritol triacrylate 38. 38 polyethylene glycol (M.G, about 400) diacrylate 10 10 t-butyl anthraquinone 3.5 3.5 methylenebis (1,1-di-t-butyl-4,4'-dimethylphenol). 0.5 0> 5 tribromomethylphenyl sulfone 3.5 3.5 Victoria pure blue 0.05 0.07 Leuco crystal violet 0.3 0.3 methyl ethyl ketone 40 40 The compositions of V-11 and Comparative Example 3 are on a laminate covered with copper, which was previously cleaned by polishing, applied so that a film thickness of 50 μm is obtained after drying. To drying at 80 ° C. for 10 minutes, the surface is covered with a poly (ethylene terephthalate) film (25 / µm thick) and coated with ultraviolet light from a 2 kW ultra-high pressure mercury lamp for 25 seconds through a step tray. (21 steps, manufactured by Eastman Kodak Co., Ltd.) exposed. After standing for 30 minutes, the resulting Element developed with 1,1,1-trichloroethane. The ST stage numbers after development are given in Table X.

Table X Number of ST stages V-11 7.8 Comparative Example 3 5.9 From table X follows that the aliphatic amino group in the polymer (a) has a great effect in improving the sensitivity.

As explained above, the photosensitive ones of the present invention have Masses have a high degree of sensitivity and excellent resistance to the Plating to be used as a plating resist or an etching resist can be.

Claims (22)

Photo-sensitive resin compound Patent claims 1. Photo-sensitive resin compound, characterized in that it is (a) a polymer which imparts a film-forming property to the resin compound and which is produced by using as comonomer a monomer which contains an aliphatic amino group and is represented by the formula: in which R1, R2 and R3 independently represent hydrogen or a methyl group, R4 and R5 independently represent an alkyl group having 1 to 4 carbon atoms or wherein R4 and R5 together with the nitrogen atom form a saturated alicyclic 4- to 7-membered ring , and n represents 0 or an integer from 1 to 3, (b) an ethylenically unsaturated compound, (c) a photosensitizer and / or a photosensitizer system capable of generating free radicals by actinic light, and (d) an organic halogen compound . 2. Composition according to claim 1, characterized in that g e k e n n -z e i c h n e t that the polymer of component (a) of the monomer of formula (1) in a Amount derived from 0.1 to 10 wt .-%. 3. Composition according to claim 1 or 2, characterized in that g e -k e n n z e i c h n e t that the monomer of the formula (1) is N, N-dialkylaminoethyl acrylate or N, N-dialkylaminoethyl methacrylate is. 4. Composition according to claim 2, characterized in that g e k e n n -z e i c h n e t that the monomer of formula (1) dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate or diethylaminoethyl methacrylate. 5. Composition according to claim 1, characterized in that g e k e n n -z e i c h n e t that component (d) is an aliphatic halogen compound. 6. Composition according to claim 5, characterized in that g e k e n n -z e i c h n e t that the aliphatic halogen compound has at least one carbon atom which is bonded to two or more halogen atoms. 7. Composition according to claim 1, characterized in that g e k e n n -z e i c h n e t that component (d) is an organic bromine compound. 8. Composition according to claim 1, characterized in that g e k e n n -z e i c h n e t that the component (d) is an organic halogen compound having a tribromomethyl group is. 9. Composition according to claim 1, characterized in that g e k e n n -z e i c h n e t that component (b) is an acrylate or methacrylate monomer. 10. Composition according to claim 1, characterized in that g e k e n n -z e i c h n e t, that the amount of component (a) is 30 to 80 parts by weight, the amount of component (b) 70 to 20 parts by weight, based on the total amount of 100 parts by weight and the Amount of component (c) 0.5 to 10 parts by weight and the amount of component (d) 0.2 to 10 parts by weight, with (c) and (d) each per 100 parts by weight of the sum of (a) and (b) are related. 11. Composition according to claim 1, characterized in that g e k e n n -z e i c h n e t, that component (a) differs from a monomer of formula (1) in an amount of 0.1 to 10% by weight and one or more comonomers from the methyl methacrylate group, Butyl methacrylate, lauryl methacrylate, ethyl acrylate, methyl acrylate, styrene, vinyl toluene, α-methylstyrene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and acrylamide in an amount of 99.9 to 90 wt .-% derives. 12. Photosensitive element, characterized in that it comprises a carrier film and a layer formed on the carrier film of a photosensitive resin composition, the resin composition (a) being a polymer which gives it film-forming properties and using a monomer as a comonomer, which is an aliphatic amino group represented by the formula: in which R1, R2 and R3 independently represent a hydrogen atom or a methyl group, R4 and R5 independently represent an alkyl group having 1 to 4 carbon atoms or wherein R4 and R5 together with the nitrogen atom form a saturated alicyclic 4- to 7-membered ring and n is 0 or an integer from 1 to 3, (b) an ethylenically unsaturated compound, (c) a photosensitizer and / or a Pfiotosensibilizersystem, which generate free radicals by actinic light, and (d) an organic Contains halogen compound. 13. Photosensitive element according to claim 12, characterized g e k e n It is noted that the amount of component (a) is 70 to 80 parts by weight, the lot of component (b) are 70 to 20 parts by weight, wherein the total amount is 100 parts by weight, and the amount of the component (c) 0.5 up to 10 parts by weight and the amount of component (d) is 0.2 to 10 parts by weight, where (c) and (d) each to 100 parts by weight of the total amount of (a) and (b) are related. 14. Photosensitive element according to claim 12, characterized g e k e n It is noted that the monomer of the formula (1) is N, N-dialkylaminoethyl acrylate or N, N-dialkylaminoethyl methacrylate. 15. Photosensitive element according to claim 12, characterized g e k e n It is noted that component (d) is an aliphatic halogen compound. 16. Photosensitive element according to claim 12, characterized g e k e n It is noted that the polymer of component (a) is different from the monomer of the formula (1) in an amount of 0.1 to 10% by weight. 17. Photosensitive element according to claim 12, characterized g e k e n n z e 1 c h n e t that the monomer of formula (1) dimethylaminoethyl methacrylate. Is dimethylaminoethyl acrylate or diethylaminoethyl methacrylate. 18. Photosensitive element according to claim 15, characterized g e k e n It is noted that the aliphatic halogen compound has at least one carbon atom contains, which is bonded to two or more halogen atoms. 19. Photosensitive element according to claim 12, characterized g e k e n Note that component (d) is an organic bromine compound. 20. Photosensitive element according to claim 12, characterized g e k e n It is noted that component (d) has an organic halogen compound is a tribromomethyl group. 21. A photosensitive element according to claim 12, characterized in that it is It is noted that component (b) is an acrylate or methacrylate monomer is. 22. Photosensitive element as claimed in claim 12, characterized in that it is It should be noted that component (a) differs from the monomer of formula (1) in an amount of 0.1 to 10 wt .-% and one or more comonomers from the Group methyl methacrylate, butyl methacrylate, lauryl methacrylate, ethyl acrylate, methyl acrylate, Styrene, vinyl toluene, α-methyl styrene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and acrylamide in an amount of 99.9 to 90 wt.