JPH10246956A - Image forming material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming material and an image forming method adaptable to the laser beams direct depiction method and capable of obtaining an image high in resolution and good in storage stability and operable in light rooms. SOLUTION: This image forming material contains a polymer having repeating units each represented by the formula and a polymer containing a monomer having a group capable of reacting with the thermal decomposition product of the polymer of the formula. This image forming material can enhance hardenability by adding a light absorber. In the formula, R<1> is H or a halogen atom or methyl group; and each of R<2> -R<4> is an aliphatic or aromatic group capable of containing oxygen or sulfur or nitrogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a printing plate, for example,
Regarding an image forming material and an image forming method capable of manufacturing a resist layer when manufacturing an electronic circuit such as a printed wiring board, it is possible to obtain an image having high resolution, good storage stability, and The present invention relates to an image forming material and an image forming method capable of working in a bright room.

[0002]

2. Description of the Related Art Conventionally, called a photopolymer,
A resin composition comprising a binder composed of a polymer material, a photopolymerizable monomer, a photopolymerization sensitizer, and the like is applied or coated on a substrate, and is irradiated with active light such as ultraviolet light through a negative or positive image, and is exposed to light. It is known that the above-mentioned image can be developed on a substrate by causing a chemical change in the portion that has changed the solubility in a solvent, and elute the portion having the solubility in the solvent. Used in the manufacture of boards.

At present, a printing plate is manufactured by providing a lipophilic ink-receiving layer on a base material such as an aluminum plate, a zinc plate, or paper having a hydrophilic surface, and uses a photopolymer called a PS plate. Are the most common.

In an electronic circuit used inside an electric product such as a printed wiring board, wiring is formed of a conductive material such as copper on an insulating substrate. In such a method for manufacturing an electronic circuit, a corrosion-resistant etching resist layer is provided on a conductive layer of a laminate in which a conductive layer is laminated on an insulating substrate in advance,
A subtractive method of etching away the exposed conductive layer, or an additive method of forming a conductive layer on the exposed insulating substrate by forming a conductive layer on the exposed insulating substrate after providing a corrosion-resistant plating resist layer on the insulating substrate The law is roughly divided into two.

At present, even in a method of manufacturing a printing plate, a method using a photopolymer is generally used as a method for forming an etching resist layer or a plating resist layer.

A method for producing an ink receiving layer, an etching resist layer, and a plating resist layer (hereinafter referred to as an image layer) using a photopolymer is as follows. First, a photopolymer is coated on a base material such as a metal plate, a laminated plate, an insulating substrate, and paper. I do. Next, the photopolymer is irradiated with light to cause a chemical change to change the solubility in the developer. Photopolymers are classified into two types according to the type of chemical change. The negative type, which becomes insoluble in the developer by polymerizing and curing the light-irradiated part, and conversely, the functional group in the photopolymer at the light-irradiated part changes, resulting in a solubility in the developer. Is a positive type. In any case, the developer insoluble in the developer remaining on the substrate after the treatment with the developer becomes the image layer.

When forming an image layer using a photopolymer, the exposure method is one of the important factors that determine the resolution. Conventionally, as an exposure method, a contact exposure method using ultraviolet light or white light via a mask has been mainly used. However, as electronic circuits and printing plates are required to be denser, finer, and shorter in manufacturing time, data is sent directly from the computer to the exposure equipment (computer-to-plate), and the photopolymer is converted using a laser. A shift to a direct exposure method is being pursued.

In order to cope with this laser direct writing method, the optical sensitivity of the photopolymer must be increased. In photopolymer, because of the photochemical reaction involved,
The optical sensitivity is low, several to several hundred mJ / cm ² . Therefore, the laser output device must have a high output, and there have been problems such as an increase in size of the device and an increase in cost.

The photochemical reaction of the photopolymer proceeds even under room light or sunlight. Also, the reactivity changes even at high temperatures. In addition, the presence of oxygen becomes an inhibitor of the reaction. Therefore, the photopolymer has a drawback that the preservation before the exposure step, the step of coating the substrate, and the like must be performed in the dark or under a safety light or under a low oxygen concentration.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a printing plate or an electronic circuit manufacturing technique which can obtain an image having a high resolution and can cope with a laser direct drawing method. An object of the present invention is to provide a forming material and an image forming method. Further, the present invention relates to an image forming material and an image forming method which have good storability and are excellent in workability such that an image can be obtained even in a bright room.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found the following invention.

The first image forming material of the present invention is an image forming material containing at least a polymer containing a repeating unit represented by the following general formula (1).

[0013]

Embedded image

In the formula, R ¹ represents a group selected from hydrogen, methyl and halogen, and R ² , R ³ and R ⁴ represent an aliphatic group or an aromatic group (however, oxygen, sulfur and nitrogen can be contained. ).

The second image forming material of the present invention comprises a polymer containing at least a repeating unit represented by the following general formula (1), and a monomer having a group capable of reacting with a thermal decomposition product of the polymer. And a polymer containing the same.

[0016]

Embedded image

In the formula, R ¹ represents a group selected from hydrogen, methyl, and halogen, and R ² , R ^3, and R ⁴ represent an aliphatic group or an aromatic group (provided that oxygen, sulfur, and nitrogen can be contained. ).

Further, a heat pattern is supplied to the image forming material in an image-like manner, the image forming material supplied with heat by the heat pattern is cured, and then the uncured image forming material is removed to form an image. This is an image forming method to be formed.

Further, in the above-mentioned image forming method, the supply of the heat pattern is performed by laser scanning controlled by image information.

The image-forming material of the present invention may contain oxygen, sunlight,
Very stable against indoor light. Therefore, it can be stored in a bright room or under oxygen. The image forming step can also be performed in a bright room.

In the image forming method of the present invention, the image forming material in the image area is cured by a laser,
An image having a very high resolution can be obtained. In addition, high productivity can be obtained by performing a laser direct writing method corresponding to a computer to plate.

The image forming material of the present invention and the image forming method related to the image forming method contain a light absorbing agent so that the image forming material in the image area can be cured by heat,
Energy such as light can be efficiently absorbed. Therefore, for example, when curing is performed with a laser, the laser may have a low output, and the apparatus cost and the operation cost can be kept low.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The image forming material and the image forming method of the present invention will be described below in detail.

The first image forming material of the present invention contains at least a polymer containing a repeating unit represented by the general formula (1).

[0025]

Embedded image

In the formula, R ¹ represents a group selected from hydrogen, methyl and halogen, and R ² , R ³ and R ⁴ represent an aliphatic group or an aromatic group (provided that oxygen, sulfur and nitrogen can be contained. ).

In the general formula (1), examples of the aliphatic group represented by R ² , R ³ and R ⁴ include an alkyl group having 1 to 18 carbon atoms [eg, methyl, ethyl, propyl, octyl, stearyl group, etc.], hydroxyalkyl Groups [e.g. hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl,
C such as 2-hydroxypropyl and 4-hydroxybutyl
₁ -C ₄ hydroxyalkyl group; and these alkoxy (C _{1 ~C 6)} substituted groups, such as 2-hydroxy -
3-butoxypropyl group, etc.], and aromatic groups include aryl groups [eg, phenyl, tolyl, xylyl groups, etc.], C
₁ -C ₄ aryl hydroxyalkyl group (such as phenyl)
Or a group substituted with an allyloxy (such as phenoxy) [for example, a 2-hydroxy-3-phenoxypropyl group, a 2-hydroxy-2-phenylethyl group, and the like].
R ² , R ³ and R ⁴ may be all the same or different. Further, R ² and R ³ may combine to form a heterocyclic ring together with the nitrogen atom.

The polymer containing a repeating unit represented by the general formula (1) is composed of units of a polymerizable unsaturated monomer containing an amine imide group and other polymerizable monomers used as required.

Specific examples of the polymerizable unsaturated monomer having an amine imide group include 1,1,1-trimethylamine methacrylimide, 1,1-dimethyl-1-ethylamine methacrylimide, and 1,1-dimethyl. -1- (2
-Hydroxypropyl) amine methacrylimide, 1,
1-dimethyl-1- (2-hydroxy-3-allyloxypropyl) amine methacrylimide, 1,1-dimethyl-1- (2'-phenyl-2'-hydroxyethyl)
Amine methacrylimide, 1,1-dimethyl-1- (2
'-Hydroxy-3'-phenoxypropyl) amine methacrylimide, 1,1,1-trimethylamine acrylimide and the like. In particular, 1,1-dimethyl-1
-(2-Hydroxypropyl) amine methacrylimide and 1,1-dimethyl-1- (2-hydroxy-3-allyloxypropyl) amine methacrylimide are preferred in terms of curability, film properties, and the like.

In addition, the Journal of Polymer Science Pa
rt A-1 Vol.6,363-373 (1968) / 2197-2207 (1968) /Vol.9,3
453-3470 (1971), The Journal of Organic Chemistry V
ol. 33, No. 4, April, 1374-1378 (1968), Macromolecules V
ol.1, No.3,253-260 (1968) /Vol.3,No.6,715-722 (1970),
Journal of Applied Polymer Science Vol.15,2609-262
1 (1971), Chemical Reviews Vol. 73, No. 3, 255-281 (197
3) 、 Ind, Eng, Chem., Prod.Res.Develp.Vol.19, No.3,338-
349 (1980), Fine Chemical Vol. 14, No. 22, 12-24 (19
85) and the like, but may be any polymerizable unsaturated monomer containing an amine imide group, but is not limited thereto as long as it is a polymerizable unsaturated monomer containing an amine imide group. . These may be used alone or in combination of two or more.

The amount of the polymerizable unsaturated monomer containing an amine imide group contained in the polymer containing the repeating unit represented by the general formula (1) in the present invention is not particularly limited. From the viewpoint, from 2 to 100 mol%, preferably from 20 to 100 mol%, more preferably from 50 to 1 mol%.
00 mol%.

The other polymerizable monomer constituting the image-forming material of the present invention is not particularly limited as long as it can be copolymerized with the above-mentioned polymerizable unsaturated monomer containing an amine imide group. For example, a carboxyl group-containing monomer [eg, (meth) acrylic acid, maleic anhydride, etc.], a (meth) acrylate ester [eg, methyl (meth) acrylate,
Ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, etc., aromatic vinyl monomers [eg, styrene, α-methylstyrene, α-chlorostyrene, etc.], halogen Containing monomers [vinyl chloride, vinylidene chloride etc.], alkyl or cycloalkyl vinyl ethers [methyl vinyl ether, cyclohexyl vinyl ether etc.], vinyl esters [vinyl acetate etc.], amide group containing monomers [for example,
(Meth) acrylamide, fumaric diamide, etc.]. These polymerizable monomers may be used alone or in combination of two or more.

The polymer containing a repeating unit represented by the general formula (1) used in the present invention generally has a molecular weight of 1,000.
~ 500,000, preferably 5,000 ~ 100,0
00. When the molecular weight is less than 1,000, film formability tends to be poor, and when it exceeds 500,000, developability tends to be poor.

When the polymer is heated to 130 ° C. or higher,
The amine imide group is decomposed to form an isocyanate group and a tertiary amine. This changes the solubility of the polymer in the solvent. In addition, the generated isocyanate group can be cross-linked by reacting with an active hydrogen-containing group or an epoxy group to form a network.

As the polymer relating to the second image forming material of the present invention, a polymer containing a monomer having a group capable of reacting with a thermal decomposition product of a polymer containing a repeating unit represented by the above general formula (1) Is an epoxy group, in order to express reactivity with a polymer having an isocyanate group which is a thermal decomposition product,
A polymerizable unsaturated monomer having a hydroxyl group, an amino group and the like is contained at least as a monomer component. In addition, various monomers may be copolymerized to control the film strength and the like.

In the image forming material of the present invention, various pigments and polymer additives are used together with other additives as secondary components. Examples of the pigment include silica, colloidal silica, alumina, alumina sol, magnesium carbonate, calcium carbonate, titanium oxide, zinc oxide and the like. Polymer additives include starch and modified products thereof, gelatin and modified products thereof, polyvinyl alcohol and modified products thereof,
Polyvinylpyrrolidone, carboxymethylcellulose,
Hydroxyethyl cellulose, sodium polyacrylate,
Sodium alginate, water-soluble polymers such as polyacrylamide, acrylic emulsion, vinyl acetate emulsion,
Emulsions such as styrene-butadiene rubber (SBR) latex and nitrile butyl rubber (NBR) latex are exemplified. Other additives include surfactants, antioxidants, plasticizers, defoamers, leveling agents, preservatives, viscosity stabilizers, pH regulators, and the like.

The image forming material of the present invention can be prepared by dipping, rod coating, bar coating, roll coating, curtain coating, slide hopper coating, screen printing, spraying, electrostatic spraying, air knife, By a conventional method such as a blade coating method, an extrusion die coating method, and an electrodeposition method, it is possible to apply directly onto a substrate or a printed wiring board to be processed and protected. The thickness of the film is in the range of 0.5 to 50 μm, more preferably 1 to 20 μm, because when the thickness is small, the mechanical strength is insufficient and the film becomes brittle, and when the thickness is large, the resolution is reduced. A range is preferred.

The coating may be carried out by dissolving the image forming material in a solvent, if necessary. Examples of the solvent include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, acetonitrile, methyl cellosolve acetate, ethyl cellosolve acetate, carbitol acetate, cyclohexanone, methyl cellosolve, propylene glycol monomethyl ether, and propylene glycol. Monomethyl ether acetate, methylene chloride, 1,1,1-trichloroethane, dimethylformamide, tetrahydrofuran and the like can be mentioned. These solvents may be used alone or as a mixture of two or more.

The base material for the image forming material and the image forming method of the present invention is, for example, a plastic plate such as polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, paper, an aluminum plate, a zinc plate when a printing plate is manufactured. And a metal plate such as a copper / aluminum plate. When manufacturing electronic circuits such as printed wiring boards, epoxy resin-impregnated glass substrate, epoxy resin-impregnated paper substrate, phenol resin-impregnated glass substrate, phenol resin-impregnated paper substrate, polyimide film And an insulating substrate such as a polyester film, a laminated plate or a metal plate provided with a conductive layer of copper, aluminum, silver, iron, gold or the like on at least one surface of the insulating substrate.

Further, an overcoat layer may be provided to protect the image forming material, or an undercoat layer made of a single layer or a plurality of layers of pigments or resins may be provided between the image forming material and the substrate. . Further, on the surface of the substrate opposite to the surface on which the image forming material is provided, a back coat layer may be provided for the purpose of curling prevention, antistatic and the like, and furthermore, an adhesive process or the like may be performed. .

In the image forming method of the present invention, the image forming material supplies a thermal pattern in an image form, and the image forming material supplied with the thermal pattern is cured. Examples of a method for supplying a thermal pattern include a thermal head, a thermal pen, flash exposure using a xenon lamp, and laser exposure. To use computer-to-plate to increase productivity, it is desirable to use a laser for curing. Lasers include carbon dioxide laser, nitrogen gas laser, argon laser, He-Ne
Laser, gas laser such as He-Cd laser, Kr laser, liquid (dye) laser, ruby laser, N
d: solid-state laser such as YAG laser, GaAs / Ga
Semiconductor lasers such as AlAs and InGaAs lasers,
KrF laser, XeCl laser, XeF laser,
An excimer laser such as Ar ₂ can be used.

In the image forming material and the image forming method of the present invention, in order to improve the curing ability of the image forming material, the image forming material preferably contains a light absorbing agent. This allows the imaging material to be cured with less heat or light energy. Light absorbers include, for example, carbon black, natural and artificial graphite, cyanine, metal-free or metal phthalocyanine,
Metal dithiolene, anthraquinone and the like can be used.

When a light absorber is selected, it is preferable to select a material having a high extinction coefficient with respect to the wavelength of the irradiation light such as a semiconductor laser beam and a high photothermal conversion efficiency.

Finally, in the image forming material and the image forming method of the present invention, a heat pattern is supplied in an image form, and the uncured portion of the image formed material cured in an image form is removed with water or an organic solvent. Then, an image layer is formed and used as various printing plates, resist films and the like.

[0045]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it departs from the gist.

Example 1 Polymer Containing Repeating Unit Having Amineimide Group
200 g of pure water was placed in a 500 ml heatable and coolable reaction vessel equipped with a synthesis thermometer, a stirrer, a cooling pipe and a dropper of (a)
And heated to 78 ° C. To this, 1,1 in 30 g of pure water
-A mixture of 15.0 g of dimethyl-1- (2-hydroxypropyl) amine methacrylimide, 6.2 g of acrylamide and 1.0 g of 2,2'-azobis (isobutyronitrile) was added dropwise over about 3 hours. did. After stirring for about 3 hours while maintaining the temperature of 78 ° C., 0.4 g of 2,2′-azobis (isobutyronitrile) is added, and stirring is further continued for 3 hours to obtain a polymer containing a desired repeating unit having an amine imide group. A solution of coalescence (a) was obtained.

Image forming layer : White polyethylene terephthalate (P) having a thickness of 188 μm.
ET) The solution of the above (a) was applied to a sheet by a rod coating method, and then dried at 80 ° C. for 10 minutes to obtain an image forming layer (thickness: 3.2 μm).

Formation of Image Layer Printing was performed with an applied pulse of 1.1 milliseconds and an applied voltage of 26 volts using an Okura Electric Facsimile Testing Machine (TH-PMD), and the image forming material corresponding to the image area was cured. And then spray water (liquid temperature 20 ° C.) (2.0 kg /
cm ² ), and the image forming material in the non-image area was removed to obtain an image layer. Observation of the image layer with a microscope revealed that the image had high resolution without any missing image portions and no stain on non-image portions.

Storage test The white PET sheet on which the image forming material was formed was stored in a bright room at 30 ° C. for 6 months, and then an image layer was formed in the same manner as described above. An image layer could be obtained.

Example 2 Synthesis of polymer (b) having a hydroxyl group in the side chain 200 g of isopropyl alcohol was placed in a reaction vessel equipped with the same apparatus as in Example 1, and the temperature was raised to 78 ° C. to this,
N-butyl acrylate 1 in 30 g of isopropyl alcohol
5.0 g and 5.4 g of 2-hydroxyethyl methacrylate
And 1.0 g of 2,2'-azobis (isobutyronitrile)
Was added dropwise over about 3 hours. After stirring for about 3 hours while maintaining at 78 ° C., 0.4 g of 2,2′-azobis (isobutyronitrile) is added, and stirring is further continued for 3 hours to obtain a polymer having a desired hydroxyl group in a side chain. (B)
Was obtained.

Formation of Image Forming Layer 5 g of the solution (a) obtained in Example 1, 5 g of the above solution (b) and a carbon black dispersion (WN manufactured by Dainichi Seika Co., Ltd.)
GK794) was mixed with 0.5 g of a white polyethylene terephthalate (PET) sheet having a thickness of 188 μm by a rod coating method and then dried at 80 ° C. for 10 minutes to obtain an image forming layer (4.6 μm in thickness). Was.

Formation of Image Layer Printing was performed under the same conditions as in Example 1 using a facsimile tester (TH-PMD) manufactured by Okura Electric Co., and the image forming material corresponding to the image area was cured. ° C) spray (2.0 kg / cm ² )
Then, the image forming material in the non-image area was removed to obtain an image layer. When the image layer was observed with a microscope,
The image had a high resolution with no stain on the non-image portion.

Storage test The white PET sheet on which the image forming material was formed was stored in a bright room at 30 ° C. for 6 months, and then an image layer was formed in the same manner as described above. An image layer could be obtained.

Example 3 Formation of Image Forming Layer 5 g of the solution (a) obtained in Example 1, 5 g of the solution (b) obtained in Example 2, and a carbon black dispersion (Dainichi Seika Co., Ltd.) 1.0 kg of WGK794) manufactured by
An 8 μm white polyethylene terephthalate (PET) sheet was applied by a rod coating method and dried at 80 ° C. for 10 minutes to obtain an image forming layer (2.8 μm in thickness).

Formation of Image Layer An image forming material corresponding to an image portion is cured by a semiconductor laser exposure device (780 nm), and then sprayed with isopropyl alcohol (liquid temperature: 20 ° C.) (2.0 kg / c).
m ² ), and the image forming material in the non-image area was removed to obtain an image layer. Observation of the image layer with a microscope revealed that the image had high resolution without any missing image portions and no stain on non-image portions.

Storage test The white PET sheet on which the image forming material was formed was stored in a bright room at 30 ° C. for 6 months, and then an image layer was formed in the same manner as described above. An image layer could be obtained.

Comparative Example White polyethylene terephthalate (P) having a thickness of 188 μm
ET) A dry film photoresist (manufactured by Nippon Synthetic Chemical Co., Ltd.) as a photopolymer was thermocompression-bonded on the sheet. This photopolymer was exposed with the same semiconductor laser exposure apparatus as in Example 3, but no photopolymerization reaction could be caused, and no image could be obtained. Also,
When a dry film resist was thermocompression-bonded to the substrate and stored at 30 ° C. in a bright room for 3 months, the polymerization reaction proceeded and the photosensitive properties were deactivated.

[0058]

As described above, the image forming material of the present invention has better storage stability than the conventional image forming material using a photopolymer. Further, in the image forming material and the image forming method of the present invention, it is possible to easily form an image by a direct drawing method using a low output laser. Therefore, excellent curing that an image having high resolution can be obtained is provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/027 H05K 3/06 H H05K 3/06 3/18 D 3/18 H01L 21/30 502R

Claims (5)

[Claims] 1. An image-forming material containing at least a polymer containing a repeating unit represented by the following general formula (1). Embedded image [Wherein, R ¹ represents a group selected from hydrogen, methyl, and halogen, and R ² , R ^3, and R ⁴ represent an aliphatic group or an aromatic group (provided that oxygen, sulfur, and nitrogen can be contained. )
Represents] 2. A polymer containing at least a polymer containing a repeating unit represented by the following general formula (1) and a polymer containing a monomer having a group capable of reacting with a thermal decomposition product of the polymer. Image forming materials. Embedded image [Wherein, R ¹ represents a group selected from hydrogen, methyl, and halogen, and R ² , R ^3, and R ⁴ represent an aliphatic group or an aromatic group (provided that oxygen, sulfur, and nitrogen can be contained. )
Represents] 3. The image forming material according to claim 1, further comprising a light absorbing agent. 4. An image-forming heat pattern is supplied to the image-forming material according to claim 1, and the image-forming material supplied with heat by the heat pattern is cured, and then an uncured image is formed. An image forming method for forming an image by removing a forming material. 5. The image forming method according to claim 4, wherein the supply of the thermal pattern is performed by laser scanning controlled by image information.