TWI421639B - Pattern forming material, pattern forming device, and pattern forming method - Google Patents

Description

Pattern forming material, pattern forming device, and pattern forming method

The present invention relates to a pattern forming material suitable for dry film photoresist (DFR) or the like, a pattern forming apparatus including the pattern forming material, and a pattern forming method using the pattern forming material.

Conventionally, when a pattern such as a wiring pattern is formed, a pattern forming material which forms a photosensitive layer by applying a photosensitive resin composition onto a support and drying it is used.

In the method for producing the pattern, for example, a layered body is formed by laminating the pattern forming material on a substrate such as a copper-area laminate on which the pattern is to be formed, and the photosensitive layer in the laminated body is formed by photolithography or the like. The layer is exposed, and after the exposure, the photosensitive layer is developed to form a pattern, and then an etching treatment or the like is performed to form the pattern.

In recent years, electronic devices have been required to be smaller, thinner, and lighter as represented by mobile communication devices, and have been required to have high performance, high performance, high quality, and high reliability. The electronic component modules of electronic machines are required to be small, high-density, and have been required to increase production efficiency with the demand for mass production.

In the above-mentioned pattern forming material, high quality, high definition, and high density are also required. When the substrate and the pattern forming material are adhered, adhesion is prevented in order to prevent bubbles and fine impurities (dirt). Therefore, it is proposed to have a buffer layer, a non-adhesive resin layer, and an adhesive photosensitive layer on the support film, thereby improving adhesion to form a high fineness in which the interlayer adhesion between the buffer layer and the adhesive resin is minimized. The purpose of the pattern (refer to Japanese Laid-Open Patent Publication No. 2003-307845).

However, in the case of improving the adhesiveness in the above-mentioned Patent Document 1, it is necessary to remove the above-mentioned adhesive photosensitive layer at the time of development, and it is also necessary to remove the above-mentioned adhesive resin, so that the development time becomes long, and Since it is inevitable that scum is generated in the developing liquid after development, the developing liquid is easily fatigued, which causes a problem of deterioration in productivity.

Further, a sensitivity of the photosensitive composition used for the pattern forming material has been proposed, and the resolution is improved by laser exposure to obtain a high-definition pattern (refer to Japanese Laid-Open Patent Publication No. 2002-303971).

However, in order to achieve the high sensitivity of the photosensitive composition used in the pattern forming material, it is necessary to improve the sensitivity of the kind of the compound contained in the photosensitive composition, the mixing ratio of the compound, and the like. When the melt viscosity of the photosensitive composition at room temperature is increased by the above-described mixing or the like, when the protective film is peeled off from the pattern forming material and the pattern forming material is laminated on the substrate, peeling of the protective film occurs. The trace and the photosensitive layer are peeled off from the support, and the productivity is deteriorated.

Therefore, the current situation is that it is not possible to provide a photosensitive composition which is suitable for the melt viscosity of the photosensitive composition, and does not cause peeling of the protective film when the laminate is formed on the substrate by the pattern forming material. a pattern forming material capable of smoothly peeling off a protective film, capable of forming a pattern with good efficiency, and obtaining a high-sensitivity and high-definition pattern, and failing to provide a pattern forming apparatus having the pattern forming material, and using one of the foregoing The pattern forming method of the pattern forming material is desired to be further improved.

The present invention has been made in view of the above-mentioned circumstances, and has been made to solve the aforementioned problems and achieve the following objects. That is, the object of the present invention is to provide a photosensitive composition having a melt viscosity at room temperature which is suitable and which can suppress the decrease in sensitivity of the photosensitive layer while forming a laminate on the substrate by the pattern forming material. A pattern forming material capable of smoothly peeling off a protective film, capable of smoothly peeling off a protective film, forming a pattern with good efficiency, and obtaining a high-sensitivity and high-definition pattern, and providing a pattern forming device including the pattern forming material, A pattern forming method of forming a material using the foregoing pattern.

The pattern forming material of the present invention is characterized in that at least a photosensitive layer is formed on the support, and the photosensitive layer is composed of a photosensitive composition containing an alkali-soluble binder, a polymerizable monomer, and a photopolymerization initiator. The photosensitive composition has a melt viscosity of from 10 ° C to 40 ° C of from 1 × 10 ⁴ to 1 × 10 ⁷ mPa. s, the minimum exposure amount under laser light having a wavelength of 405 nm when the pattern thickness obtained by subjecting the photosensitive layer to exposure development is 90% of the thickness of the unexposed state is 20 mJ/cm 2 or less.

Further, the pattern forming material of the present invention is characterized in that at least a photosensitive layer is formed on the support, and the photosensitive layer is composed of a photosensitive composition containing an alkali-soluble binder, a polymerizable monomer, and a photopolymerization initiator. The ratio of the total weight of the alkali-soluble binder to the polymerizable monomer is 1:0.90 to 1:0.70, and when the pattern thickness obtained by subjecting the photosensitive layer to exposure development is 90% of the thickness of the unexposed state, The minimum exposure amount under laser light having a wavelength of 405 nm is 20 mJ/cm ² or less.

A pattern forming apparatus according to the present invention is characterized by comprising a pattern forming material, a light irradiation mechanism having at least illuminable light, and a light modulating light from the light irradiation means, and a photosensitive layer in the pattern forming material The light modulation mechanism for performing exposure includes the pattern forming method of the present invention, comprising at least exposing and developing the photosensitive layer in the pattern forming material.

[The best way to implement the invention] (patterning material)

The pattern forming material of the present invention is characterized in that the photosensitive layer on the support is composed of a photosensitive composition, and the photosensitive composition has a melt viscosity of from 1 × 10 ⁴ to 1 × 10 at 30 ° C to 40 ° C. ⁷ mPa. s, when the pattern thickness obtained by exposing the photosensitive layer to 90% of the thickness of the unexposed state, the pattern formation of a minimum exposure amount under a laser light having a wavelength of 405 nm is 20 mJ/cm ² or less material.

<Photosensitive composition>

The photosensitive composition described above contains an alkali-soluble binder, a polymerizable monomer, a photopolymerization initiator, and other components appropriately selected as occasion demands, and the photosensitive layer formed of the photosensitive composition is exposed. When the thickness of the pattern obtained by the development becomes 90% of the thickness of the unexposed state, the minimum exposure amount under laser light having a wavelength of 405 nm is 20 mJ/cm ² or less.

-Alkali Soluble Binder -

The above-mentioned alkali-soluble binder is preferably, for example, a wet-swellable property to an alkaline liquid, and more preferably soluble in an alkaline liquid.

As the binder which exhibits wet expansion or solubility in the alkaline liquid, for example, those having an acidic base are suitable, for example.

The acidic group is not particularly limited and may be appropriately selected depending on the purpose. For example, it may be a carboxyl group, a sulfonic acid group, a phosphoric acid group or the like, and among these, a carboxyl group is preferred.

The alkali-soluble binder having a carboxyl group may, for example, be an ethylene-based copolymer having a carboxyl group, a polyurethane resin, a poly-proline resin, a modified epoxy resin, or the like. The ethylene-based copolymer having a carboxyl group is preferred from the viewpoints of solubility in a coating solvent, solubility in an alkali developing solution, suitability, and ease of adjustment of film properties.

The ethylene-based copolymer having a carboxyl group may, for example, be obtained by copolymerizing at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable with the above; For example, it may be a compound described in Paragraph Nos. [0164] to [0207] of JP-A-2005-25841.

-Polymerizable monomer -

The above-mentioned polymerizable monomer is not particularly limited, and may be appropriately selected according to the purpose, but, for example, a monomer having at least one of a polyurethane group and an aryl group is suitable, for example. Or oligomer. Moreover, it is preferable to have two or more types of polymerizable groups.

The above polymerizable group may be, for example, an ethylenically unsaturated bond (for example, (meth) acrylonitrile, (meth) acrylamide, styrene, vinyl, vinyl ether, etc.) A allylic group such as a vinyl group, an allyl ether or an allyl group, or a polymerizable cyclic ether group (for example, an epoxy group or an oxetanyl group). Among these, it is preferably an ethylenically unsaturated bond, and for example, it may be a compound described in Paragraph Nos. [0210] to [0285] of JP-A-2005-258431.

Further, in order to adjust the exposure sensitivity and the light-sensing wavelength at the time of exposure to the photosensitive layer to be described later, a sensitizer may be added in addition to the photopolymerization initiator described above.

The sensitizer described above can be appropriately selected from visible light, ultraviolet light, visible light laser or the like as a light irradiation mechanism to be described later.

The sensitizer described above can be excited by an active energy ray, and interacts with other substances (for example, a radical generator, an acid generator, etc.) (for example, energy movement, electron movement, etc.). A useful group for generating a radical or an acid or the like.

The addition of the aforementioned sensitizer is preferably a minimum exposure amount under laser light having a wavelength of 405 nm when the thickness of the pattern obtained by subjecting the photosensitive layer to exposure development becomes 90% of the thickness of the unexposed state. It becomes 20 mJ/cm ² or less.

The aforementioned sensitizer is not particularly limited and may be appropriately selected from known sensitizers; for example, it may be a well-known polynuclear aromatic compound (for example, ruthenium, osmium, tri-o-phenylene). , xanthene (for example, luciferin, eosin, erythromycin, rhodamine B, rose bengal), cyanine (for example, quinolinol carbocyanine, thioquinoline carbocyanine, quinoline Carnation cyanine), merocyanines (eg, merocyanine, carbocyanine), thianes (eg, Lloyd's violet, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroform) , quercetin), terpenoids (eg, quinone), square steroids (eg, square 鎓), acridone (eg, acridone, chloroacridone, N-methylacridone) , N-butylacridone, N-butyl-chloroacridone, 2-chloro-10-butylacridone, etc.), coumarins (for example, 3-(2-benzofuran) - 7-diethylamino coumarin, 3-(2-benzofuranyl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidene-7-diethyl Amino coumarin, 3-(2-methoxybenzimidyl)-7-diethylamine Coumarin, 3-(4-dimethylaminobenzimidyl)-7-diethylamino coumarin, 3,3'-carbonyl bis(5,7-di-n-carboxycoumarin ,3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzylidene-7-methoxycoumarin, 3-(2-furanyl)-7 -diethylamino coumarin, 3-(4-diethylaminocinnamino)-7-diethylamino coumarin, 7-methoxy-3-(3-pyridylcarbonyl) Coumarin, 3-benzylidene-5,7-dipropoxycoumarin, etc., in addition to Japanese Patent Laid-Open No. 5-19475, JP-A-7-271028, JP-A-2002-363206, JP-2002 The coumarin compound or the like described in each of the publications of JP-A-2002-363208, JP-A-2002-363209, and the like.

The combination of the photopolymerization initiator and the sensitizer described above is, for example, an electron-transporting initiator as described in JP-A-2001-305734 [(1) Electron supply initiator And a combination of sensitizing dyes, (2) electron-accepting initiators and sensitizing dyes, (3) electron-donating initiators, sensitizing dyes, and electron-accepting initiators (ternary starting systems) .

The content of the sensitizer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, particularly preferably 0.2 to 10% by mass, based on the total components of the photosensitive resin composition. When the content is less than 0.05% by mass, the sensitivity to the active energy ray is lowered, the exposure process takes time, and the productivity is lowered, and when it exceeds 30% by mass, the aforementioned sensitization during storage The agent will be chromatographed from the aforementioned photoreceptor.

The photopolymerization initiator may be used singly or in combination of two or more.

Particularly preferred examples of the photopolymerization initiator are, for example, the above-mentioned phosphine oxides, the aforementioned α-aminoalkyl group which can correspond to laser light having a wavelength of 405 nm in the exposure described later. A ketone, a halogenated hydrocarbon compound having the above three skeletons, a composite photoinitiator in combination with an amine compound which is a sensitizer described later, a hexaarylbiimidazole compound, or a titanium metallocene.

The content of the photopolymerization initiator in the photosensitive composition is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, particularly preferably 2 to 10% by mass.

-Other ingredients -

The other components mentioned above may be, for example, a thermal polymerization inhibitor, a plasticizer, a color former, a colorant, etc.; and further, a adhesion promoter and other auxiliary agents on the surface of the substrate may be further used in combination. (for example, pigments, conductive particles, fillers, antifoaming agents, flame retardants, levelers, release inhibitors, antioxidants, perfumes, thermal crosslinking agents, surface tension modifiers, moving agents, etc.). For example, the compound may be, for example, the compound described in paragraphs [0316] to [0336] of JP-A-2005-258431; by appropriately containing such components, an adjustment pattern can be achieved. The purpose of forming the properties of the material such as stability, photogenicity, burning property, and film properties.

<The melt viscosity of the photosensitive composition>

The melt viscosity of the photosensitive composition is not particularly limited, and may be appropriately selected according to the purpose, for example, the melt viscosity of the photosensitive composition at 30 ° C to 40 ° C, using a coating device The melt viscosity when the photosensitive composition solution is applied to a support.

The value of the melt viscosity is not particularly limited and may be appropriately selected according to the purpose, for example, at 30 ° C to 40 ° C, preferably 1 × 10 ⁴ ~ 1 × 10 ⁷ mPa. s, more preferably 1 × 10 ⁵ ~ 1 × 10 ⁷ mPa. s, when the aforementioned melt viscosity is less than 1 × 10 ⁴ Pa. When s, it will become too soft, and peeling marks will occur when the protective film is peeled off from the pattern forming material, when it exceeds 1 × 10 ⁷ mPa. In the case of s, the build-up function is lowered, the flexibility at the time of lamination is not good, and the laminate is not uniformly formed, and when the protective film is peeled off from the support, the above-mentioned photosensitive layer is simultaneously peeled off from the support.

- Determination of melt viscosity -

The aforementioned measurement of the melt viscosity was carried out using a viscometer. The viscosity meter described above is not particularly limited and may be appropriately selected depending on the purpose. For example, (1) it may be determined according to the Hagen-Poisol method to determine the amount of the sample required to flow out through the capillary. Capillary viscometer for time; (2) Bubble viscometer, drop viscometer, Heppler viscometer, viscosity meter for the falling velocity or bubble rising velocity of the specimen in the mountain sample according to the Stoke rule; (3) Rotational viscometer, visco viscometer, plate viscometer, and blood flow velocity meter for viscosity resistance received by objects in the fluid.

The coating method of the photosensitive composition solution may be, for example, a spray method, a roll coating method, a spin coating method, a slit coating method, an etching coating method, an air curtain coating method, a die coating method, or a concave coating method. Various coating methods such as a method, a wire coating method, and a knife coating method.

The coating apparatus described above is not particularly limited, and may be appropriately selected according to the purpose, and may be, for example, a disperser system in which a coating liquid is mixed and automatically applied, a Stark mixer, a micro mixer, A coating device or the like in which a tube mixing device, a liquid feeding device, and the like are combined.

The drying of the photosensitive layer formed after the application is different depending on the components, the type of the solvent, the ratio of use, and the like. However, for example, it can be dried by a drying device at a temperature of 60 to 110 ° C for 30 seconds to 15 seconds. Allow it to dry in minutes.

- Support -

The above-mentioned support is not particularly limited, and may be appropriately selected depending on the purpose. However, it is preferable that the photosensitive layer can be peeled off and the light transmittance is good, and it is more preferable that the surface is excellent in smoothness.

The aforementioned support is preferably a synthetic resin and is transparent. For example, it may be polyethylene terephthalate, polyethylene folate, polypropylene, polyethylene, cellulose triacetate, diacetic acid. Cellulose, alkyl (meth)acrylate, poly(meth)acrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinyl chloride copolymer, polyfluorene Amine, polyimine, vinyl chloride. Various plastic films such as vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film, and nylon film. These may be used alone or in combination of two or more.

In addition, the support body described in the above-mentioned support can be used, for example, in the above-mentioned support, which is described in Japanese Laid-Open Patent Publication No. Hei 5- No. Hei. .

The thickness of the aforementioned support is not particularly limited and may be appropriately selected depending on the purpose; for example, it is preferably 4 to 300 μm, more preferably 5 to 175 μm.

The shape of the aforementioned support body is not particularly limited, and may be appropriately selected depending on the purpose; for example, it is preferably elongated. The length of the aforementioned elongated support is not particularly limited, and for example, it may be from 10 meters to 20,000 meters.

-Photosensitive layer -

The position at which the photosensitive layer is provided in the photosensitive film is not particularly limited, and may be appropriately selected depending on the purpose, and is usually laminated on the support.

The thickness of the photosensitive layer is not particularly limited and may be appropriately selected according to the purpose, and is, for example, preferably from 3 to 100 μm, more preferably from 5 to 70 μm.

In the above-mentioned photosensitive layer, it is preferable to perform light modulation by a light modulation mechanism having n pixel portions that receive light emitted from the light irradiation means, and then reuse the light. Exposure is performed by arranging light of a microlens array having aspherical microlenses that can correct aberrations due to distortion of the exit surface in the pixel portion.

<other layer>

The other layers described above are not particularly limited and may be appropriately selected depending on the purpose; for example, a protective film, a buffer layer, an oxygen barrier layer (PC layer), a release layer, an adhesive layer, a light absorbing layer, and a surface are formed. The steps of protecting the layers and the like.

The buffer layer described above does not have a viscosity at normal temperature, and the layer is formed as a layer of melt flow under vacuum and heating conditions. The aforementioned PC layer is usually formed of polyvinyl alcohol as a main component of 1.5 micrometers.

- Protective film -

The protective film can prevent the above-mentioned photosensitive layer from being stained and damaged, and has a protective function.

The position of the protective film to be disposed in the pattern forming material is not particularly limited and may be appropriately selected depending on the purpose; it is usually provided on the photosensitive layer.

The protective film may be, for example, a material used on the support, a polyoxynized paper, a paper laminated with polypropylene or polyethylene, a polyolefin or a polytetrafluoroethylene sheet, or the like. Among these, a polyethylene film or a polypropylene film is preferred.

The thickness of the protective film is not particularly limited and may be appropriately selected depending on the purpose; for example, it is preferably 5 to 100 μm, more preferably 8 to 30 μm.

In the case of using the protective film described above, the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film preferably have the relationship of adhesive force A and adhesive force B. .

The combination of the foregoing support and the protective film (support/protective film), for example, may be (polyethylene terephthalate/polypropylene) or (polyethylene terephthalate/polyethylene) , (polyvinyl chloride / cellophane), (polyimide / polypropylene), and (polyethylene terephthalate / polyethylene terephthalate). Further, by performing surface treatment on at least one of the support and the protective film, the adhesive force can satisfy the above relationship. The surface treatment of the support body is, for example, an undercoat layer, a corona discharge treatment, a flame treatment, an ultraviolet irradiation treatment, and an adhesion strength to the photosensitive layer; and an example of the surface treatment includes the undercoat layer deposition. High-frequency wave irradiation treatment, glow discharge treatment, active plasma irradiation treatment, and laser light treatment.

Further, the static friction coefficient between the support and the protective film is preferably from 0.3 to 1.4, more preferably from 0.5 to 1.2.

When the aforementioned static friction coefficient is less than 0.3, the winding gap may be generated in the case of forming a reel due to excessive slidability; and when it exceeds 1.4, it is difficult to roll into a good reel shape.

The pattern forming material described above, for example, a core wound in a cylindrical shape, is preferably in the form of a long roll. The length of the long strip-shaped pattern forming material is not particularly limited, and may be appropriately selected from, for example, a range of 10 meters to 20,000 meters. Further, in order to make it easy for the user to use, it is also possible to form a long strip having a roll shape ranging from 100 meters to 1,000 meters in a slit shape. Further, in this case, it is preferable to wind the aforementioned support body to the outermost side. Further, the above-described rolled pattern forming material may be subdivided into a sheet shape. When storing, from the viewpoint of end face protection and corrosion prevention, it is preferable to provide a separator (especially a moisture-proof substance and a desiccant) on the end surface, and it is also preferable to use a bag and a moisture-permeable bag. Low material.

In order to adjust the adhesion between the protective film and the photosensitive layer, the protective film can also be subjected to surface treatment. In the foregoing surface treatment, for example, an undercoat layer composed of a polymer of polyorganosiloxane, fluorinated polyolefin, polyvinyl fluoride, and polyvinyl alcohol may be formed on the surface of the protective film. The undercoat layer may be formed by applying the coating liquid of the above polymer to the surface of the protective film, followed by drying at 30 ° C to 150 ° C (especially 50 ° C to 120 ° C) for 1 to 30 minutes.

The pattern forming material of the present invention is one in which the photosensitive composition has a suitable melt viscosity at room temperature, and can suppress the decrease in the sensitivity of the photosensitive layer, and does not occur when the layered body on the substrate is formed by the pattern forming material. The peeling property of the protective film is protected, and the protective film can be smoothly peeled off, and a pattern forming material of a high-sensitivity and high-definition pattern can be obtained. Therefore, it can be widely used as a pattern for a liquid crystal display device such as a printed wiring board, a color filter, a pillar, a rib, a spacer, a partition, or the like, a hologram, a micromachine, a verification, or the like, and It can be suitably used in the pattern of the present invention and its formation method.

<pattern and pattern forming method>

The pattern of the present invention is produced by using the pattern forming method of the present invention.

In the first aspect of the pattern forming method of the present invention, the photosensitive composition of the present invention is applied onto the surface of a substrate, dried to form a photosensitive layer, and then subjected to exposure development.

Further, in the second aspect of the pattern forming method of the present invention, at least one of heating and pressurization, the pattern forming material of the present invention is laminated on the surface of the substrate, and then exposure development is performed.

Hereinafter, the description of the pattern forming method of the present invention will be made to make the pattern of the present invention more detailed.

-Substrate -

The above-mentioned substrate is not particularly limited, and a material having a surface smoothness as high as having a concave-convex surface can be appropriately selected from known materials; however, it is preferably a plate-like substrate (substrate); specifically, for example, for example, It may be a known substrate for forming a printed circuit (for example, a copper clad laminate), a glass plate (for example, an alkali glass plate), a synthetic resin resin film, paper, a metal plate, or the like. Among these, it is preferable that the substrate for forming a printed wiring board is a substrate for forming a printed wiring board from the viewpoint of performing high-density mounting of a semiconductor or the like on a multilayer wiring board or an assembly wiring board. The wiring pattern has been formed.

In the above-mentioned substrate, a laminate formed by forming a photosensitive layer on the substrate may be used as the first aspect described above, or a layer in which the photosensitive layer in the pattern forming material is overlapped may be used. And the formation of the laminate. In other words, the photosensitive layer in the laminated body may be subjected to the following exposure, and the exposed region may be cured to form a pattern by development as described later.

-Laminar body -

The method for forming the laminate according to the first aspect described above is not particularly limited, and may be appropriately selected depending on the purpose. It is preferable that the laminate is formed by coating and drying the photosensitive composition on the substrate. Floor.

The coating and drying method is not particularly limited and may be appropriately selected depending on the purpose. For example, it may be carried out when the photosensitive layer in the pattern forming material is formed, and the photosensitive composition solution may be applied. The same method as drying is carried out, for example, a method of applying the photosensitive composition solution by using a spin coater, a slit coater, a roll coater, a die coater, an air curtain coater or the like.

The method for forming the laminate of the second aspect described above is not particularly limited, and may be appropriately selected depending on the purpose. It is preferable to laminate the pattern forming material while performing at least one of heating and pressurization. On the aforementioned substrate. Further, in the case where the pattern forming material has the protective film, it is preferred that the protective film is peeled off and the photosensitive layer is laminated on the substrate.

The above heating temperature is not particularly limited and may be appropriately selected depending on the purpose, however, for example, it is preferably 70 to 130 ° C, more preferably 80 to 110 ° C.

The pressure of the pressurization is not particularly limited and may be appropriately selected according to the purpose, but is, for example, preferably 0.01 to 1.0 MPa, more preferably 0.05 to 1.0 MPa.

The apparatus for performing at least any of the above-described heating and pressurization is not particularly limited and may be appropriately selected according to the purpose, but, for example, for example, a hot rolling mill or a hot roll laminator is suitably used (for example, Manufactured by Daisuke Machine Co., Ltd., VP-II), vacuum laminator (for example, MVLP500, manufactured by Nihon Machine Co., Ltd.).

<exposure>

The purpose of the above-described exposure is to form a cured portion and an uncured portion in order to expose the photosensitive layer.

The object to be exposed is not particularly limited as long as it is a material having a photosensitive layer, and may be appropriately selected depending on the purpose; for example, it is preferably formed on or formed from the aforementioned photosensitive composition on a substrate. The laminate formed by the material is carried out.

The exposure of the laminate is not particularly limited, and may be appropriately selected according to the purpose. For example, the photosensitive layer may be exposed through the support, the buffer layer, and the PC layer, or may be peeled off. After the support, the photosensitive layer is exposed through the buffer layer and the PC layer; after the support and the buffer layer are peeled off, the photosensitive layer may be exposed through the PC layer; or may be peeled off. After the support, the buffer layer, and the PC layer, the photosensitive layer is exposed.

Although the aforementioned exposure is not particularly limited, it may be appropriately selected according to the purpose, however, for example, it is preferably a digital exposure, an analog exposure, or the like; among these, digital exposure is preferred.

The aforementioned digital exposure is not particularly limited, and may be appropriately selected according to the needs of the object. However, for example, it is preferable to generate a control signal based on the formed pattern forming information, and to use light modulated according to the control signal. Come on.

The above-described digital exposure mechanism is not particularly limited and may be appropriately selected according to the purpose. However, for example, it is preferable to modulate the light from the light based on the light irradiation mechanism of the illumination light and the formed pattern formation information. The light modulation mechanism of the light irradiated by the illumination mechanism.

<Light modulation mechanism>

The above-described light modulation means is not particularly limited as long as it can modulate light, and can be appropriately selected according to the purpose. For example, it is preferable to have n pixel parts.

The above-described light modulation mechanism having n pixel portions is not particularly limited and may be appropriately selected depending on the purpose; for example, it is preferably a spatial light modulation element.

For example, a spatial light modulation device (SLM, Special Light Modulator) having a digital microlens device (DMD) or a MEMS (Micro Electro Mechanical Systems) type is suitable. A special optical modulator), an optical element (PLZT element) that modulates transmitted light by an electro-optical effect, a liquid crystal shutter (FLC), etc., among which, for example, a DMD is preferable.

Further, the optical modulation mechanism described above is preferably a pattern signal generating means having a factory control signal based on the formed pattern information. In this case, the optical modulation mechanism described above can modulate the light with a control signal generated by the pattern signal generating means.

The aforementioned control signal is not particularly limited and may be appropriately selected depending on the purpose of the object; for example, a suitable one is a digital signal.

The optical modulation mechanism and the pattern forming apparatus including the optical modulation mechanism are, for example, examples described in paragraph numbers [0016] to [0047] of JP-A-2005-258431. Wait.

<Light Irradiation Mechanism>

The light irradiation mechanism is not particularly limited, and may be appropriately selected depending on the purpose. For example, it may be a (super) high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a photocopier, etc. A conventional light source such as a light pipe, an LED, or a semiconductor laser, or a mechanism that can synthesize two or more light beams, and among these, a mechanism that can synthesize two or more pieces of light is preferably used.

The light irradiated from the light-irradiating means may be, for example, a light-irradiating initiator or a sensitizer used by, for example, transmitting the support through the support. Activated electromagnetic waves, ultraviolet rays, visible rays, electron beams, X-rays, laser light, etc.; among them, laser light is preferred, and lasers synthesized by two or more lights are more suitable (hereinafter, referred to as " Compound wave laser"). Further, even when light irradiation is performed after peeling off the support, the same light can be used.

The wavelength of the ultraviolet to visible light is, for example, preferably 300 to 1500 nm, more preferably 320 to 800 nm, and particularly preferably 330 to 650 nm.

The wavelength of the aforementioned laser light is, for example, preferably 200 to 1500 nm, more preferably 300 to 800 nm, more preferably 330 to 500 nm, and particularly preferably 395 to 415 nm.

The mechanism for illuminating the composite laser light as described above, for example, preferably having a combination of a plurality of lasers, a multimode fiber, and a laser beam irradiated from each of the plurality of lasers on the multimode fiber The mechanism of the optical system.

In the following, for example, the mechanism (fiber array light source) that can illuminate the composite laser light can be, for example, an example described in paragraph numbers [0130] to [0177] of JP-A-316431.

<Microlens array>

In the above-described exposure, it is preferred that the modulated light is passed through the microlens array, or further, the fiber array, the imaging optical system, or the like may be used.

The microlens array described above is not particularly limited, and may be appropriately selected according to the needs of the object. However, for example, it is suitable for the aberration to be corrected by the distortion of the exit surface in the pixel portion. Aspherical microlens.

The aspherical surface described above is not particularly limited, and may be appropriately selected according to the purpose, but is preferably a toric surface.

Hereinafter, the description will be made with reference to the drawings relating to the microlens array, the aperture array, the imaging optical system, and the like.

Fig. 3(A) shows a lens system (imaging optical system) 454, 458, which corresponds to the DMD 50, by a DMD 50, a light irradiation mechanism 144 that irradiates the DMD 50 with laser light, and a lens system (imaging optical system) 454, 458 that expands the laser light reflected by the DMD 50. A microlens array 472 having a plurality of microlenses 474, an aperture array 476 corresponding to the microlenses 472, and an aperture array 476 having a plurality of openings 478, and a lens system for imaging the laser light passing through the openings to the exposed surface 56 (imaging) Optical system) 480, 482 formed by the exposure head.

Here, Fig. 4 shows the measurement results of the flatness of the reflecting surface of the microlens 62 constituting the DMD 50. In the same figure, the height points are connected to indicate the same height position of the reflecting surface, and the distance between the contour lines is 5 nm. Further, the x direction and the y direction shown in the figure are two diagonal directions of the microlens 62, and the microlens 62 is rotated as described above with the rotation axis extending in the y direction as the center. Further, the fifth (A) and fifth (B) drawings each show the displacement of the height of the reflection surface of the microlens 62 along the x direction and the y direction.

As shown in Fig. 4 and Fig. 5, there is a distortion on the reflecting surface of the microlens 62. Especially in the central portion of the viewing lens, the distortion in one diagonal direction (y direction) is better than the other pair. The distortion in the angular direction (x direction) is still large. Therefore, the condensing position of the laser light B condensed by the microlens 55a of the microlens array 55 causes a problem of shape distortion.

In the pattern forming method of the present invention, in order to prevent the aforementioned problem, the microlens 55a of the microlens array 55 has a special shape different from the conventional one. This point is explained in detail below.

The sixth (A) and sixth (B) drawings show the front shape and the side surface shape of the entire microlens array 55 in detail. In these figures, the dimensions of the various portions of the microlens array 55 are also described, and the units are in mm (mm). In the pattern forming method of the present invention, 1024 x 256 columns of microlenses 62 of the DMD 50 are driven as described in the second drawing referred to above, and the microlens array 55 corresponding thereto is in the horizontal direction. The microlens 55a of 1024 rows and 256 columns are arranged side by side in the direction and the longitudinal direction, respectively. Further, in the diagram (A) of the same figure, the side-by-side order of the microlenses 55 is denoted by j in the lateral direction and denoted by k in the longitudinal direction.

Further, the seventh (A) and seventh (B) drawings each show the front shape and the side surface shape of one microlens 55a in the microlens array 55. Further, the contour lines of the microlens 55a are shown together in the figure (A) of the same figure. The end surface of the light exit surface of each microlens 55a is an aspherical shape that corrects aberration due to distortion of the reflecting surface of the microlens 62. More specifically, the microlens 55a is a toric lens having a curvature radius Rx of −0.125 mm corresponding to the x-direction optics and a radius of curvature Ry=−0.1 mm corresponding to the y direction.

Therefore, the condensed states of the laser light B in the cross section parallel to the x direction and the y direction are approximately as shown in Figs. 8(A) and 8(B), respectively. That is, when compared with the inside of the cross section parallel to the y direction in the cross section parallel to the x direction, the microlens 55a in the latter cross section has a small radius of curvature and a short focal length.

When the microlens 55a has the above shape, the beam diameter in the vicinity of the condensing position (focus position) of the microlens 55a is calculated by computer simulation as shown in Figs. 9a, b, c, and d. Further, for comparison, the same simulation calculation was performed in the case where the microlens 55a has a spherical shape having a radius of curvature Rx = Ry = -0.1 mm, and the results are shown in Figs. 10a, b, c, and d. Further, the value of z in each drawing is such that the evaluation position of the focus direction of the microlens 55a is expressed by the distance from the light beam exit surface of the microlens 55a.

Further, the surface shape of the microlens 55a used in the above simulation calculation is calculated by the following calculation formula.

In the above calculation formula, Cx represents the curvature in the x direction (=1/Rx), Cy represents the curvature in the y direction (=1/Ry), and x represents the distance from the optical axis O of the lens in the x direction, and the Y system The distance from the optical axis O of the lens in the y direction.

Comparing the 9th to dth graphs and the 10th to dth graphs, the pattern forming method of the present invention has a toric surface having a small focal length in a cross section parallel to the x direction in which the microlens 55a is parallel to the y direction. The lens suppresses the distortion of the shape of the beam near the condensing position. Thereby, an image having no distortion and higher definition is exposed on the photosensitive layer 150. Further, in the present embodiment shown in Figs. 9a to d, it is understood that the beam diameter is small in a wide range, that is, the depth of focus is large.

Further, regarding the magnitude relationship between the distortion of the central portion of the microlens 62 in the x direction and the y direction, contrary to the above, the focal length in the cross section parallel to the x direction is smaller than the focal length in the cross section parallel to the y direction. When the toric lens constitutes a microlens, the undistorted, higher-definition image is similarly exposed on the photosensitive layer 150.

Further, the array of openings 59 arranged in the vicinity of the condensing position of the microlens array 55 is arranged such that only light passing through the corresponding microlens 55a is incident on each opening 59a. That is, by providing the opening array 59, it is possible to prevent light from the adjacent microlenses 55a not corresponding thereto from being incident on the respective openings 59a, and the extinction ratio can be improved.

When the value of the diameter of the opening 59a of the opening array 59 which is originally provided for the above purpose is as small as a certain degree, the effect of suppressing the distortion of the beam shape in the condensing position of the microlens 55a can be obtained. However, this increases the amount of light blocked by the aperture array 59 and reduces the light use efficiency. On the other hand, when the microlens 55a has an aspherical shape, since the light is not blocked, a high light retention efficiency can be obtained.

Further, in the pattern forming method of the present invention, the microlens 55a may have a 2-dimensional aspherical shape or an aspherical shape of a higher order (4th order, 6th order...). By adopting the aforementioned high-dimensional aspherical shape, a more high-definition beam shape can be obtained.

Further, in the embodiment described above, the light-emitting side end surface of the microlens 55a is an aspherical surface (toric surface), but one of the two types of light passes through one end surface and becomes a spherical surface, and the other becomes a cylindrical surface microlens. The same effects as in the above embodiment can be obtained by constituting the microlens array.

Further, in the above-described embodiment, the microlens 55a of the microlens array 55 is an aspherical shape that corrects the aberration due to the distortion of the reflecting surface of the microlens 62, but the microlens array is formed. The same effect can be obtained by replacing the refractive index distribution of the aberration due to the distortion of the reflecting surface of the microlens 62 on the lens instead of using the aspherical shape.

An example of the microlens 155a is as shown in Fig. 11. The front and side shapes of the microlens 155a are shown in each of the drawings (A) and (B). As shown in the figure, the outer shape of the microlens 155a is a parallel plate shape. In addition, the x and y directions in the same figure are as described above.

Further, the 12th (A) and (B) drawings roughly show the condensed state of the laser beam B in the cross section parallel to the x direction and the y direction by the microlens 155a. The microlens 155a has a refractive index distribution which gradually increases from the optical axis O toward the outside, and the broken line shown in the microlens 155a in the same figure indicates a position which changes from the optical axis O by a certain equal pitch. As shown in the figure, in the cross section parallel to the x direction and the cross section parallel to the y direction, the refractive index change ratio of the microlens 155a in the latter section is large, and the focal length is short. The same effect as that of the microlens array 55 described above can be obtained by using the microlens array composed of the refractive index distribution type lens.

Further, in the microlens having the aspherical surface shape of the microlens 55a shown in the previous FIGS. 7 and 8 and having the refractive index distribution as described above, both the surface shape and the refractive index distribution can correct the cause. The aberration caused by the distortion of the reflecting surface of the microlens 62.

Further, in the above-described embodiment, the aberration due to the distortion of the reflecting surface of the microlens 62 constituting the DMD 50 can be corrected, but in the pattern forming method of the present invention using the spatial light modulation element other than the DMD, even the space When there is distortion on the surface of the pixel portion of the light modulation element, the aberration of the distortion can be corrected by using the present invention, and the shape of the beam can be prevented from being deformed.

Next, the aforementioned imaging optical system will be further explained.

When the exposure head is irradiated with the laser light from the light irradiation means 144, the cross-sectional area of the beam line reflected by the DMD 50 in the opening direction is expanded by several times (for example, twice) via the lens systems 454 and 458. The expanded laser light is concentrated by the respective microlenses of the microlens array 472 corresponding to the respective pixel portions of the DMD 50 through the openings corresponding to the array of openings 476. The exposed laser light is imaged onto the exposed surface 56 via lens systems 480, 482.

In the imaging optical system, the laser light reflected by the DMD 50 is projected on the exposure surface 56 by being expanded by several times by the enlarged lenses 454 and 458, so that the entire image range is expanded. At this time, if the microlens array 472 and the aperture array 476 are not disposed, as shown in FIG. 3(B), the pixel size (dot size) of each beam spot BS projected on the exposure surface 56 corresponds to the exposure. The size of the area 468 indicates that the MTF (Modulation Transfer Function) characteristic of the sharpness of the exposure area 468 is lowered.

On the other hand, in the case where the microlens array 472 and the aperture array 476 are disposed, the laser light reflected by the DMD 50 is concentrated by the respective microlenses of the microlens array 472 corresponding to the respective pixel portions of the DMD 50. Thereby, as shown in FIG. 3(C), even when the exposure area is enlarged, the dot size of each beam spot BS can be reduced to a desired size (for example, 10 μm×10 μm), and the MTF characteristic can be prevented from being lowered. Perform high-definition exposure. Further, the inclination of the exposure region 468 is such that the DMD 50 is disposed obliquely without a gap between the pixels.

Moreover, even if the light beam is thickened due to the aberration of the microlens, the beam size can be shaped by the aperture array on the exposed surface 56 to a certain size, while the aperture array is provided by corresponding to each pixel. To prevent crosstalk between adjacent pixels.

Further, by using the high-intensity light source in the light irradiation means 144, since the angle of the light beam incident on the respective lenticular surfaces of the microlens array 472 from the lens 458 becomes small, it is possible to prevent the light beams of the adjacent pixels from being incident. That is, a high extinction ratio can be achieved.

<Other optical systems>

The pattern forming method of the present invention may be used in combination with other optical systems suitably selected from conventional optical systems. For example, it may be, for example, a light amount distribution correcting optical system formed by a pair of combined lenses.

In the light quantity distribution correction optical system described above, the beam width at each of the emission positions is changed, and the ratio of the beam width near the central portion of the optical axis to the beam width of the peripheral portion is smaller than the incident side on the emission side, and further When the parallel light beam of the light irradiation means is irradiated to the DMD, the light quantity distribution on the illuminated surface is corrected to be approximately uniform. Regarding the aforementioned light amount distribution correction optical system, for example, it may be special. The contents described in paragraph numbers [0090] to [0105] of the publication No. 2005-258431 are issued.

<other steps>

The other steps described above are not particularly limited, and may be appropriately selected, for example, from the steps of forming a pattern; for example, it may be a developing step, an etching step, a plating step, or the like. These may be used alone or in combination of two or more.

The developing step is a step of exposing the photosensitive layer in the pattern forming material by the exposure step, hardening the exposed region of the photosensitive layer, removing the unhardened region, and developing the pattern to form a pattern. .

The aforementioned development step can be carried out, for example, by means of development.

The development step described above is not particularly limited as long as it can be developed using a developing solution, and may be appropriately selected according to the purpose. However, for example, it may be the aforementioned developing solution. The spraying means, the means for applying the developing liquid, the means for impregnating the developing liquid, and the like. These may be used alone or in combination of two or more.

Further, the developing means may include a developing solution exchange means for exchanging the developing liquid, a developing liquid supply means for supplying the developing liquid, and the like.

The developing solution is not particularly limited, and may be appropriately selected according to the purpose. However, for example, it may be an alkaline liquid, a water-based developing liquid, an organic solvent, or the like; among them, It is preferably a weakly alkaline aqueous solution. The alkali component of the weakly alkaline liquid may be, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate or potassium hydrogencarbonate. Sodium phosphate, potassium phosphate, potassium pyrophosphate, borax, and the like.

The pH of the aforementioned weakly alkaline aqueous solution is, for example, preferably from about 8 to 12, more preferably from about 9 to 11. The weakly basic aqueous solution may be, for example, 0.1 to 5% by mass of an aqueous solution of sodium carbonate or an aqueous solution of potassium carbonate.

The temperature of the developing solution may be appropriately selected from those of the photosensitive layer. However, for example, it is preferably about 25 to 40 °C.

The above-mentioned developing solution may also be used in combination with a surfactant, an antifoaming agent, or an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethyleneamine, morpholine, triethanolamine, etc.). Or an organic solvent (for example, an alcohol, a ketone, an ester, an ether, a guanamine, a lactone, etc.) for promoting development. Further, the developing solution may be a water-based developing solution obtained by mixing water or an aqueous alkali solution with an organic solvent, or may be a single organic solvent.

The etching step described above can be carried out by a method appropriately selected from a conventional etching treatment method.

The etching liquid used in the etching treatment is not particularly limited, and may be appropriately selected according to the purpose. However, for example, in the case where the metal layer is formed of copper, for example, it may be a copper chloride solution, A ferric chloride solution, an alkali etching solution, a hydrogen peroxide-based etching liquid, or the like; among these, from the viewpoint of an etching factor, a ferric chloride solution is preferred.

The pattern can be formed on the surface of the substrate by removing the pattern after the etching step in the etching step.

The above-described pattern is not particularly limited, and may be appropriately selected according to the purpose, but, for example, a wiring pattern or the like is suitable, for example.

The plating step described above can be carried out by selecting an appropriate method from the conventional plating treatment.

For example, the plating treatment may be copper plating such as copper sulfate plating or copper pyrophosphate plating, solder plating such as rapid solder plating, or watt bath (nickel sulfate-nickel chloride) plating. Treatment such as nickel plating, hard gold plating, soft gold plating, etc., such as nickel sulfonate.

The pattern is removed by the plating step and the pattern is removed, and an unnecessary portion is removed by an etching treatment or the like as needed, and a permanent pattern can be formed on the surface of the substrate.

[Manufacturing Method of Printed Wiring Board and Color Filter]

The pattern forming method of the present invention can be used for the production of a printed wiring board, particularly a printed wiring board having a hole portion such as a through hole or a through hole, and the production of a color filter. Hereinafter, an example of a method of manufacturing a printed wiring board and a color filter by the pattern forming method of the present invention will be described.

-Manufacturing method of printed wiring board -

In particular, a method for producing a printed wiring board having a hole portion such as a through hole or a through hole can be obtained by (1) forming a pattern forming material on a substrate for forming a printed wiring board having a hole portion as the substrate. The photosensitive layer is formed by laminating the positional relationship on the substrate side, and (2) is irradiated with light in a desired region from the opposite side of the substrate of the laminate to harden the photosensitive layer, and (3) from the laminate The support, the buffer layer, and the barrier layer of the pattern forming material are removed, and (4) the photosensitive layer of the laminate is developed, and the unhardened portion of the laminate is removed to form a pattern.

Further, the removal of the support described in the above (3) may be performed between the above (1) and (2) instead of the above (2) and (4).

Then, in order to obtain a printed wiring board, a method of etching or plating the substrate for forming a printed wiring board can be used (for example, a conventional subtraction or addition method (for example, a half addition, a full addition method) using the pattern formed as described above. In the case of forming a printed wiring board by a masking process which is advantageous for the industry, the above-described subtraction method is preferred. After the treatment, the cured resin remaining on the printed wiring board forming substrate is peeled off, and In the case of the above-mentioned subtraction, a desired printed wiring board can be produced by etching the copper thin film portion after peeling. Further, the multilayer printed wiring board can be produced in the same manner as the above-described printed wiring board.

Next, a method of manufacturing a printed wiring board having through holes using the pattern forming material will be further explained.

First, a substrate for forming a printed wiring board having a through hole and having a surface covered with a metal plating layer is prepared. In the above-mentioned substrate for forming a printed wiring board, for example, a substrate on which a copper plating layer is formed on an insulating substrate such as a copper-clad laminate or a glass-epoxy resin, or an interlayer insulating film is laminated on the substrate to form a copper plating. A coated substrate (laminated substrate).

Next, in the case where the protective layer is provided on the pattern forming material, the protective film peeled off on the pattern layer material is pressed by a pressure roller to connect the photosensitive layer of the pattern forming material to the printed wiring. On the surface of the substrate for forming a plate (layering step). Thereby, a laminate having the substrate for forming a printed wiring board and the laminate in this order is obtained.

The lamination temperature of the pattern forming material is not particularly limited. For example, it may be room temperature (15 to 30 ° C) or heating (30 to 180 ° C), and among them, it is preferable to heat. Lower (60~140°C).

The rolling pressure of the aforementioned pressure roller is not particularly limited, and is, for example, preferably 0.1 to 1 MPa.

The speed of the aforementioned pressing is not particularly limited, and is preferably 1 to 3 meters per minute.

Further, the substrate for forming a printed wiring board may be previously heated, or may be laminated under reduced pressure.

In the formation of the above-mentioned laminated body, the pattern forming material may be laminated on the printed wiring board forming substrate, or may be directly coated with a photosensitive resin composition solution for producing the pattern forming material. The surface of the printed wiring board forming substrate is dried and the photosensitive layer, the barrier layer, the buffer layer, and the support volume layer are formed on the printed wiring board forming substrate.

Then, light is irradiated from the surface on the side opposite to the substrate of the above laminated body to cure the photosensitive layer. Further, in this case, depending on the case (for example, when the light transmittance of the support is insufficient), the exposure may be performed after peeling off the support.

At this time, when the support, the buffer layer, and the barrier layer are not peeled off, the support, the buffer layer, and the barrier layer are peeled off from the laminate (peeling step).

Then, the uncured region of the photosensitive layer on the substrate for forming a printed wiring board is dissolved and removed by a suitable developing solution to form a pattern of the hardened layer for forming a metal layer for the wiring pattern forming hard layer and the via hole, and A metal layer is exposed on the surface of the substrate for forming a printed wiring board (developing step).

Further, the treatment for promoting the hardening reaction of the hardened portion can be performed by performing post-heat treatment or post-exposure treatment as necessary after development. The development process may be the aforementioned wet development method or a dry development method.

Next, the metal layer exposed on the surface of the substrate for forming a printed wiring board is dissolved and removed by an etching solution (etching step). Since the opening of the through hole is covered by the hardened resin composition (masking film), the etching liquid does not enter the void and corrodes the metal plating in the through hole, so that the metal plating of the through hole remains in a specific shape. Thereby, a wiring pattern can be formed on the substrate for forming a printed wiring board.

The foregoing etching liquid is not particularly limited, and may be appropriately selected according to the purpose, but, for example, in the case where the metal layer is formed of copper, it may be a copper chloride solution or a ferric chloride solution. An alkali etching solution, a hydrogen peroxide-based etching liquid, or the like; among these, from the viewpoint of an etching factor, a ferric chloride solution is preferred.

Then, the hardened layer (hardened material removing step) which is a release sheet is removed from the printed wiring board forming substrate by a strong alkali aqueous solution or the like.

The alkali component of the above-mentioned strong alkali aqueous solution is not particularly limited, and for example, it may be sodium hydroxide, potassium hydroxide or the like.

The pH of the aqueous alkali solution is preferably, for example, about 12 to 14, more preferably about 13 to 14.

The above-mentioned strong alkali aqueous solution is not particularly limited, and for example, it may be a 1 to 10% by mass aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution.

Further, the printed wiring board may be a printed wiring board having a plurality of layers.

Furthermore, the pattern forming material can be used not only in the etching process but also in the plating process. For example, the plating method may be copper plating such as copper sulfate plating or copper pyrophosphate plating, solder plating such as rapid solder plating, or watt bath (nickel sulfate-nickel chloride) plating. Nickel plating such as nickel sulfonate, hard gold plating, gold plating such as soft gold plating, and the like.

-Manufacturing method of color filter -

When the photosensitive layer of the pattern forming material of the present invention is bonded to a substrate such as a glass substrate, and the support, the buffer layer, and the barrier layer are peeled off from the pattern forming material, the support (film) charged may be present. The person receives an unpleasant electrical shock, or there is a problem that the charged support itself has dust adhesion. Therefore, it is preferable to provide a conductive layer on the support or to perform a process of imparting conductivity to the support itself. Further, in the case where the conductive layer is provided on the support opposite to the buffer layer, it is preferable to provide a hydrophobic polymer layer to improve the scratch resistance.

Next, a pattern forming material having a red photosensitive layer in which each of the photosensitive layers is colored red, green, blue, and black, a pattern forming material having a green photosensitive layer, a pattern forming material having a blue photosensitive layer, and a black have been prepared. A pattern forming material of the photosensitive layer. A pattern forming material having the red photosensitive layer for red pixels is used, and a red photosensitive layer is laminated on the surface of the substrate to form a laminated body, and then exposed to an image pattern to be developed to form a red pixel. After the formation of the red pixel is formed, the aforementioned laminate is heated to harden the uncured portion. The green and blue pixels can also be processed in the same way, so that each pixel is formed.

The layered body may be formed by laminating the pattern forming material on the glass substrate as described above, or by directly applying the photosensitive resin composition solution or the like for producing the pattern forming material described above. On the glass substrate, a photosensitive layer, a barrier layer, a buffer layer, and a support are laminated on the glass substrate by drying. Further, in the case of arranging three kinds of pixels such as red, green, and blue, it may be arranged in a mosaic type, a triangle type, or a four-pixel configuration type.

A pattern forming material having the black photosensitive layer is laminated on the surface on which the pixel is formed, and a rear side of the pixel side is exposed and developed to form a black matrix. The uncured portion can be hardened by heating the laminate in which the black matrix is formed to produce a color filter.

In the pattern forming method of the present invention, since the peeling development can be performed at the interface between the photosensitive layer and the barrier layer, it is possible to suppress the staining of the developing liquid after development and to repeatedly use the developing liquid or the like. The advantage. Further, since it is not necessary to remove the barrier layer and the buffer layer described above during development, it is advantageous in that the development time is short.

Since the pattern forming method of the present invention uses the pattern forming material of the present invention, it can be used for pattern formation of various patterns, wiring patterns, etc., color filters, pillars, ribs, spacers, The manufacture of liquid crystal structural parts such as a partition wall, the manufacture of holograms, micro-machines, verification, etc., are particularly suitable for use in high-definition wiring pattern formation. Since the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, it can be used for pattern formation of various pattern formations, wiring patterns, and the like, color filters, pillars, ribs, spacers, partition walls, and the like. The manufacture of structural members, the manufacture of holograms, micromachines, and verification are particularly suitable for the formation of high-definition wiring patterns and color filters.

[Examples]

Hereinafter, the present invention will be further specifically described by the examples, but the present invention is not limited by the following examples.

(Example 1) <Preparation of photosensitive composition solution>

Each of the following components was mixed to prepare a photosensitive composition solution having an M/B ratio of 1:0.80.

. Morphine. . . . . . . . . . . . . . . . 0.013 parts by mass. Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate methacrylic acid (copolymer composition (mass ratio): 50/20/7/23, mass average molecular weight: 90,000, acid value: 150) . . . . . . . . . . 15 parts by mass. Addition of 1/2 molar ratio of hexamethylene diisocyanate and tetraethylene oxide monomethacrylate. . . . . . . . . . . . . . 6.0 parts by mass. N-butyl-2 chloro-methyl acridone. . . . . . . . . 0.05 parts by weight. 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd., BPE-500). . . . . . . . . . . . 6.0 parts by weight. 2,2-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. 2.17 parts by mass. Victoria Blue. . . . . . . . . . . . . . 0.02 parts by mass. Hidden crystal violet. . . . . . . . . . . . . . 0.26 parts by mass. Methyl ethyl ketone. . . . . . . . . . . . . . 40 parts by mass. 1-methoxy-2-propanol. . . . . . . . . . . . 20 parts by mass

- Production of pattern forming materials -

As shown in Fig. 1, a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., 16QS52) was used as the support 1 described above, and the aforementioned photosensitive resin was composed by a bar coater. The solution was coated on the support 1 and dried in a hot air circulating dryer at 80 ° C for 30 minutes to form a photosensitive layer 2 having a thickness of about 15 μm after drying, followed by lamination on the photosensitive layer. The aforementioned protective film 3 of a polypropylene film having a thickness of 20 μm.

<Formation of pattern> -Production of laminated body -

Next, the surface of the copper clad laminate (without through holes and having a copper thickness of 12 μm) which was subjected to wiring as described above was subjected to chemical polishing treatment and prepared. In the copper clad laminate, the photosensitive layer of the pattern forming material is bonded to the copper clad layer, and the protective film in the photosensitive film is peeled off, and an automatic cutting laminator (MACH730, Bodong) is used. The laminates of the company are laminated to form a laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) are laminated in this order. Pressing conditions: the temperature of the laminating roller was 105 ° C, the pressure of the laminating roller was 0.3 MPa, and the laminating speed was 1 m/min.

<Evaluation of Protective Film Peelability>

The surface of the photosensitive layer after the peeling property of the protective film was observed by a reflection microscope, and the presence or absence of peeling marks was evaluated. The results are shown in Table 3.

◎: no peeling marks and extremely smooth; ○: no peeling marks; ×: peeling marks such as stripes and wrinkles were observed.

<Separation of self-supporting film>

Whether or not the protective film was peeled off from the aforementioned support film was visually observed to be smoothly peeled off. The results are shown in Table 3.

◎: The protective film can be peeled off smoothly from the support film; ○: the photosensitive layer is not peeled off from the support film together with the protective film; ×: The photosensitive layer is peeled off from the support film together with the protective film.

<Measurement of Melt Viscosity>

The measurement of the melt viscosity is carried out by measuring the melt viscosity of the photosensitive composition at 35 ° C when the photosensitive composition solution is applied onto the support.

The melt viscosity measuring instrument was carried out using a flow rate meter (DAR, RECOLICA GM) at a temperature increase rate of 5 ° C / min and a frequency of 1 Hz. The measurement results are shown in Table 3.

<development time>

In the measurement of the above resolution, the development time from the spraying of the above-described developing liquid to the dissolution and removal of the aforementioned unhardened region was measured.

(1) Method for measuring the shortest development time The polyethylene terephthalate film (support), the buffer layer and the coating layer were obtained by peeling off the above-mentioned laminated body, and the temperature was 0.15 MPa at a pressure of 0.15 MPa. The mass % sodium carbonate aqueous solution was sprayed on the entire surface of the photosensitive layer on the copper clad laminate, and the time required to start spraying from the sodium carbonate aqueous solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured as the shortest image. time. The shortest imaging time is 3 seconds.

<resolution>

(2) Measurement of Sensitivity A pattern forming apparatus having a laser light source of 405 nm was used as the above-described light-emitting means at the interval of 2 ^{1 / 2} with respect to the above-mentioned photosensitive layer of the pattern forming material in the above-mentioned laminated body. Light of different light energies of 0.1 mJ/cm ² to 100 mJ/cm ² is exposed to harden a part of the aforementioned photosensitive layer. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the laminate, and the pressure of 0.15 MPa and the shortest development time obtained in the above (1) were 2 Over time, an aqueous solution of sodium carbonate (30 ° C, 1% by mass) was sprayed on the entire photosensitive layer of the copper clad laminate to dissolve and remove the unhardened region, and the thickness of the remaining hardened region was measured.

Next, the relationship between the amount of irradiation of light and the thickness of the hardened layer is plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the light energy at a thickness of 30 μm in the hardened region was determined as the light energy required to harden the photosensitive layer.

(3) Measurement of resolution The laminate was formed in the same manner and under the same conditions as the evaluation method of the shortest image time of the above (1), and allowed to stand at room temperature (23 ° C, 55% RH) for 10 minutes. From the above-mentioned polyethylene terephthalate film (support) of the obtained laminate, using the above-described pattern forming apparatus, the line width is 5 μm to 20 with a column/gap=1/1 and a 1 μm scale. The exposure of each line width up to the micron is performed with a line width of 20 μm to 50 μm on a 5 μm scale. The exposure amount at this time is the light energy necessary for curing the photosensitive layer of the pattern forming material measured in the above (2). After standing at room temperature for 10 minutes, a polyethylene terephthalate film (support) was peeled off from the above laminated body. On the entire surface of the photosensitive layer on the copper clad laminate, a sodium carbonate aqueous solution (30 ° C, as the above-mentioned developing solution) was sprayed at a pressure of 0.15 MPa and twice the shortest development time obtained in the above (1). 1% by mass) to dissolve and remove the unhardened region. The surface of the thus obtained copper-clad laminate having the cured resin pattern obtained was observed with an optical microlens, and the minimum column width without abnormalities such as clogging or waviness on the column of the cured resin pattern was measured and used as the resolution. The smaller the resolution coefficient value, the better.

<exposure speed>

Using the pattern forming apparatus described above, the relative moving speed of the exposure light and the photosensitive layer is changed, and the speed at which a general wiring pattern can be formed is obtained. The exposure was carried out from the side of the polyethylene terephthalate film (support) to the photosensitive layer of the above-mentioned laminated body. In addition, the faster the setting speed is, the pattern can be formed efficiently.

<pattern forming device>

The composite laser light source having the light irradiation mechanism as shown in FIGS. 13 to 18 and the light modulation mechanism can be controlled to drive only the main scanning as shown in FIG. Between the 1,024 microlens arrays, 768 sets of microlenses 1,024 x 256 columns of DMD 50 are arranged in the sub-scanning direction, and microlenses 474 arranged as a toric surface as shown in FIG. 3 are arranged in an array. A lens array 472 and a pattern forming device for imaging the optical systems 480, 482 of the pattern forming material by light passing through the microlens array.

<Reference Example 2>

The pattern forming material of Reference Example 2 was produced in the same manner as in Example 1 except that the M/B ratio was 1:0.80 instead of 1:0.88, and the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 3.

<Example 3>〉

The pattern forming material of Example 3 was produced in the same manner as in Example 1 except that the M/B ratio was 1:0.80 instead of 1:0.72, and the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 1> <Preparation of photosensitive composition solution>

Each of the following components was mixed to prepare a photosensitive composition solution having an M/B ratio of 1:0.93.

. Morphine. . . . . . . . . . . . . . . . 0.013 parts by mass. Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate methacrylic acid (copolymer composition (mass ratio): 50/20/7/23, mass average molecular weight: 90,000, acid value: 150) . . . . . . . . . . 15 parts by mass. Addition of 1/2 molar ratio of hexamethylene diisocyanate and tetraethylene oxide monomethacrylate. . . . . . . . . . . . . . 7.0 parts by mass. N-butyl-2 chloro-methyl acridone. . . . . . . . . 0.05 parts by weight. 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd., BPE-500). . . . . . . . . . . . 7.0 parts by weight. 2,2-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. 2.17 parts by mass. Victoria Blue. . . . . . . . . . . . . . 0.02 parts by mass. Hidden crystal violet. . . . . . . . . . . . . . 0.26 parts by mass. Methyl ethyl ketone. . . . . . . . . . . . . . 40 parts by mass. 1-methoxy-2-propanol. . . . . . . . . . . . 20 parts by mass

In the same manner as in Example 1, except that the photosensitive composition solution described above was applied to the support, the pattern forming material of Comparative Example 1 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 2> <Preparation of photosensitive composition solution>

Each of the following components was mixed to prepare a photosensitive composition solution having an M/B ratio of 1:0.65.

. Morphine. . . . . . . . . . . . . . . . 0.013 parts by mass. Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate methacrylic acid (copolymer composition (mass ratio): 50/20/7/23, mass average molecular weight: 90,000, acid value: 150) . . . . . . . . . . 15 parts by mass. Addition of 1/2 molar ratio of hexamethylene diisocyanate and tetraethylene oxide monomethacrylate. . . . . . . . . . . . . . 4.5 parts by mass. N-butyl-2 chloro-methyl acridone. . . . . . . . . 0.05 parts by weight. 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd., BPE-500). . . . . . . . . . . . 4.5 parts by weight. 2,2-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. 2.17 parts by mass. Victoria Blue. . . . . . . . . . . . . . 0.02 parts by mass. Hidden crystal violet. . . . . . . . . . . . . . 0.26 parts by mass. Methyl ethyl ketone. . . . . . . . . . . . . . 40 parts by mass. 1-methoxy-2-propanol. . . . . . . . . . . . 20 parts by mass

In the same manner as in Example 1, except that the photosensitive composition solution described above was applied to the support, the pattern forming material of Comparative Example 2 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.

From the results of Table 3, it can be understood that in Examples 1 to 3 of the pattern forming material of the present invention, the M/B ratio is in the range of 1:0.72 to 1:0.88, and the peeling trace of the unprotected film does not occur from the support. The phenomenon of peeling off the body film. It can be understood that in Comparative Example 1, when the M/B ratio is 1:0.93, the molecular weight viscosity of the photosensitive layer at 35 ° C is as low as 9.0 × 10 ³ , and peeling marks of the protective film are generated, and the photosensitive layer is formed. It will also peel off from the support film. It can be understood that in Comparative Example 2, although the above-mentioned peeling marks and peeling of the photosensitive layer did not occur, the sensitivity of the photosensitive layer was inevitably lowered to 25 mJ/cm ² .

Further, it can be understood that, according to the pattern forming material of the present invention, on the one hand, the sensitivity of the photosensitive layer can be maintained at a high sensitivity, and on the other hand, the laminator can be automatically cut to perform extremely good lamination, and the pattern can be formed with good efficiency.

According to the present invention, it is possible to provide a photosensitive composition having a melt viscosity at room temperature which is suitable, and it is possible to suppress a decrease in sensitivity of the photosensitive layer, and a protective film does not occur when a layered body is formed on the substrate by the pattern forming material. a pattern forming material capable of smoothly peeling off a protective film, capable of forming a pattern with good efficiency, and obtaining a high-sensitivity and high-definition pattern, and a pattern forming apparatus having the pattern forming material, and using the foregoing A pattern forming method of a pattern forming material.

According to the pattern forming material of the present invention, it is suitable because the melt viscosity at room temperature at which the photosensitive composition can be obtained is suitable, and the sensitivity of the photosensitive layer can be suppressed, and the layered body is formed on the substrate by the pattern forming material. When the protective film is peeled off, the protective film can be smoothly peeled off, a pattern can be formed with good efficiency, and a pattern of high-sensitivity and high-definition pattern can be obtained, so that it is suitable for use as a protective, interlayer insulating film. And can be widely used as a component of a liquid crystal display such as a printed wiring board (multilayer wiring board, assembly wiring board, etc.), a color filter, a pillar, a rib, a spacer, a partition, etc., hologram, micro It is used for pattern formation such as machine and verification.

BS. . . Beam point

1. . . Support

2. . . Photosensitive layer

3. . . Protective film

50. . . Digital microlens device (DMD)

55a. . . Microlens

55. . . Microlens array

56. . . Exposure surface

59a. . . Opening

59. . . Open array

62. . . Microlens

144. . . Light illumination mechanism

150. . . Photosensitive layer

155a. . . Microlens

454, 458. . . Lens system (imaging optical system)

468. . . Exposure area

472. . . Microlens array

474. . . Microlens

476. . . Open array

478. . . Opening

480, 482. . . Lens system (imaging optical system)

Fig. 1 is an explanatory view showing a layer configuration of a pattern forming material.

Fig. 2A is an example of a diagram showing an example of a use area of the DMD.

Fig. 2B is an example of a diagram showing an example of a use area of the DMD.

Fig. 3A is an example of a cross-sectional view along the optical axis which is different from the constitution of the other exposure heads of the optical system.

Fig. 3B is an example of a plan view showing an optical image projected on the surface to be exposed without using a microlens array or the like.

The 3Cth diagram is an example of a plan view showing an optical image projected on the surface to be exposed when a microlens array or the like is used.

Fig. 4 is an example of a graph showing distortion of a reflecting surface of a microlens constituting a DMD by a contour line.

Fig. 5A is an example of a graph showing distortion of the reflecting surface of the microlens in the diagonal direction of the two lenses.

Fig. 5B is an example of a graph showing distortion of the reflection surface of the microlens in the two diagonal directions of the lens, similar to Fig. 15A.

Fig. 6A is an example of a front view of a microlens array that can be used in a patterning device.

Fig. 6B is an example of a side view of a microlens array which can be used in a pattern forming apparatus.

Fig. 7A is an example of a front view of a microlens constituting a microlens array.

Fig. 7B is an example of a side view of a microlens constituting a microlens array.

Fig. 8A is an example of a schematic view showing one of the sections of the light collecting state of the microlens.

Fig. 8B is an example of a schematic view showing one of the sections of the light collecting state of the microlens.

Fig. 9a is an example of a graph showing a simulation result of a beam diameter in the vicinity of the collected light of the microlens of the present invention.

Fig. 9b is an example of a graph showing the simulation result at another position, similar to Fig. 9a.

Fig. 9c is an example of a graph showing a simulation result at another position, similar to Fig. 9a.

The ninth figure is an example of a graph showing the simulation result at another position as in the case of Fig. 9a.

Fig. 10a is an example of a graph showing a simulation result of a beam diameter in the vicinity of the collected light of the microlens in the conventional pattern forming method.

Fig. 10b is an example of a graph showing the simulation results at another position, similar to Fig. 10a.

Fig. 10c is an example of a graph showing a simulation result at another position, similar to Fig. 10a.

Fig. 10d is an example of a graph showing a simulation result at another position, similar to Fig. 10a.

Fig. 11A is an example of a front view of a microlens constituting a microlens array.

Fig. 11B is an example of a side view of a microlens constituting a microlens array.

Fig. 12A is an example of a schematic view showing one of the sections of the light collecting state of the microlens.

Fig. 12B is an example of a schematic view in another section of the light collecting state of the microlens.

(A) in Fig. 13a is a perspective view showing a configuration of a fiber array light source; (B) is an example of a partially enlarged view of (A); (C) and (D) are light-emitting points in a laser emitting portion. An example of a plan of the arrangement.

Fig. 13b is an example of a plan view showing the arrangement of the light-emitting points in the laser emitting portion of the fiber array light source.

Fig. 14 is a view showing an example of the structure of the multimode optical fiber.

Fig. 15 is a view showing an example of a plan view of a composite laser light source.

Fig. 16 is an example of a plan view showing the configuration of a laser module.

Fig. 17 is a view showing an example of a side view of the configuration of the laser module shown in Fig. 16.

Figure 18 is a partial side elevational view showing the construction of the laser module shown in Figure 16.

50. . . Digital microlens device (DMD)

Claims (16)

A pattern forming material comprising at least a photosensitive layer on a support, the photosensitive layer being composed of a photosensitive composition containing an alkali-soluble binder, a polymerizable monomer, and a photopolymerization initiator, the alkali solubility The ratio of the total weight of the binder to the polymerizable monomer is 1:0.72 to 1:0.80, and the photosensitive composition has a melt viscosity of 1×10 ⁵ to 3×10 ⁶ mPa at 30° C. to 40° C. s, the minimum exposure amount under laser light having a wavelength of 405 nm when the thickness of the pattern obtained by exposure development of the photosensitive layer becomes 90% of the thickness of the unexposed state is 15 mJ/cm ² or less, wherein the alkali The soluble binder is an ethylene-based copolymer, and the polymerizable single system includes a monomer having at least one of a polyurethane group and an aryl group. The pattern forming material of claim 1, wherein the alkali-soluble binder has an acidic group. The pattern forming material according to claim 1, wherein the photopolymerization initiator comprises a halogenated hydrocarbon derivative, a phosphine oxide, a hexaarylbiimidazole, an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound. At least one selected from the group consisting of decylphosphine oxide, aromatic sulfonium salt and ketoxime ether. The pattern forming material of claim 1, which comprises a protective film on the photosensitive layer. The pattern forming material of claim 1, wherein the photosensitive layer has a thickness of 3 to 100 μm. The pattern forming material of claim 1, wherein the support system contains a synthetic resin and is transparent. The pattern forming material of claim 1, wherein the supporting system is elongated. A pattern forming apparatus comprising: a pattern forming material according to claim 1 of the patent application, wherein the light irradiation mechanism having at least illuminable light and the light from the light irradiation means are modulated, and The photosensitive layer in the pattern forming material is configured to perform an exposure light modulation mechanism. A pattern forming method comprising at least exposing and developing the photosensitive layer in the pattern forming material according to claim 1 of the patent application. The pattern forming method of claim 9, wherein the support system is formed by wiring the printed wiring board. The pattern forming method of claim 9 is characterized in that the image pattern is exposed based on the formed pattern information. The pattern forming method according to claim 9 is characterized in that the light irradiation means for irradiating light and the light modulation means for adjusting the light irradiated from the light irradiation means based on the formed pattern information are used. The light modulation mechanism is configured by a pattern signal generating mechanism that further generates a control signal based on the formed pattern information, and is modulated from the light according to a control signal generated by the pattern signal generating unit. The light irradiated by the illumination mechanism. The pattern forming method of claim 12, wherein the light modulation mechanism is composed of n pixel portions, and can be controlled by the n pixel portions along with the formed pattern information. Any of the aforementioned pixel parts of the continuous configuration is less than n. The pattern forming method of claim 9, wherein the exposure is performed using laser light having a wavelength of 395 to 415 nm. The pattern forming method of claim 9, wherein the pattern is formed after the development is performed. The pattern forming method of claim 15, wherein the pattern is a wiring pattern, and the pattern is formed by at least one of an etching treatment and a plating treatment.