WO2000058788A1

WO2000058788A1 - Photopolymerizable layered product with high resolution and semiconductor device made with the same

Info

Publication number: WO2000058788A1
Application number: PCT/JP2000/001814
Authority: WO
Inventors: Koichi Fujishiro; Shinji Inaba; Shinsuke Okita
Original assignee: Nippon Steel Chemical Co., Ltd.
Priority date: 1999-03-26
Filing date: 2000-03-24
Publication date: 2000-10-05

Abstract

A photopolymerizable layered product useful as a dry film resist (DFR); and a semiconductor device and a liquid-crystal apparatus both obtained with the layered product. The layered product comprises a photopolymerizable layer and a support layer, wherein the photopolymerizable layer comprises (A) 100 parts by weight of a resin which is a carboxylated copolymer obtained by reacting a diol compound with an acid dianhydride and has a weight-average molecular weight of 3,000 to 40,000 and an acid value of 50 to 200 mgKOH/g, (B) 25 to 180 parts by weight of an unsaturated compound having two or more photopolymerizable terminal ethylenic groups per molecule, and (C) a photopolymerization initiator. The photopolymerizable layered product not only is improved in unsusceptibility to cold flow, film flexibility and strength, substrate-conforming properties during laminating, and developability but is excellent in resolution and adhesion. Hence, a high-performance semiconductor device, display, etc. can be provided.

Description

Description High-resolution photopolymerizable laminate and semiconductor device using the same

'' (Technical field) The present invention is suitable for a solder resist, a plating resist, an etching resist for forming a circuit board, an insulating film for multilayering a wiring board on which a semiconductor element is mounted, and a photosensitive adhesive. It relates to a photopolymerizable laminate that can be re-developed. Further, the present invention relates to a semiconductor device using the same, and a display component such as a power filter and a spacer which contribute to an increase in the size of a liquid crystal display or a plasma display.

(Background technology)

Conventionally, a dry phenolic resist (hereinafter referred to as DFR) comprising a support layer and a photopolymerizable layer has been used as a resist for circuit creation. DFR is generally prepared by laminating a photopolymerizable composition on a supporting film, and in many cases, further laminating a protective film on the composition. As a material for such a photopolymerizable layer, an aluminum development type using a weak aqueous solution as a developer is generally used.

To create a printed circuit board using DFR, first peel off the protective film, then use a laminator or the like to laminate DFR on a permanent circuit board such as a copper-clad laminate, Exposure is performed through a pattern mask or the like. Next, the non-exposed portion of the photopolymerizable composition is dissolved or dispersed and removed with a developing solution, and is hardened on a substrate. To form a resist image. Thereafter, the metal surface of the substrate is subjected to etching or plating treatment using the formed resist image as a mask, and then the resist image is peeled off using an aqueous solution of an alkaline solution stronger than the developing solution. A printed wiring board is formed. Therefore, the cured film is required to have strong film strength and flexibility. On the other hand, since DFR is stored in a three-layer roll state, a phenomenon such as a so-called cold flow that the photopolymerizable layer protrudes from the end face during storage may occur. Not preferred.

In addition, if the photopolymerizable layer before exposure in DFR is hard, the adhesiveness is poor when the photopolymerizable layer is laminated on a substrate, and the photopolymerizable layer cannot fill the unevenness on a substrate having unevenness. A space may be created between the photopolymerizable layer and the substrate. When such a space is formed, the etching liquid or the plating liquid penetrates into the substrate, thereby causing defects such as disconnection or short circuit.

The photopolymerizable layer of DFR widely used at present has (1) a thermoplastic organic polymer binder, (2) at least one ethylenic group, and a polymer can be formed by a photopolymerization initiator. It is composed of a composition comprising an unsaturated compound, (3) a photopolymerization initiator, and (4) other additives. All of the thermoplastic organic polymer binders are vinyl copolymerized with several monomers having one ethylenic group in the molecule (at least one of which contains a carboxyl group). It is a system copolymer resin. That is, the polymer chain in the resin is composed of carbon-carbon bonds, and a carboxyl group, an ester thereof, or an aromatic compound is bonded as a side chain thereof. Specific examples include copolymers of methacrylic acid and its esters and styrene derivatives. On the other hand, as the unsaturated compound, aliphatic polyhydric alcohols, acrylic acid and methacrylate, are the most common, and trimethylolpropane triacrylate is most commonly used. It is known to have at least two unsaturated groups, such as acrylate, dipentaerythrene hexaacrylate, pentaerythrate monoacrylate, polyethylene diol glycol diacrylate, and the like. .

The role of the thermoplastic organic polymer binder is responsible for the film forming properties at room temperature, the flexibility as a film, and the solubility in an alkaline developer. The structure of the binder relating to these properties is widely defined as a weight average molecular weight of 20,000 to 600,000 and an acid value of 100 to 600. In general, when the molecular weight is less than 20,000, the cold flow and cut-chip properties are degraded, and when the molecular weight is as large as over 600,000, poor development and a decrease in substrate followability during heat lamination are observed. Therefore, a molecular weight range that optimizes the properties as DFR has been tried for each resin composition. Furthermore, JP-A-64-55555, JP-A-64-55551, JP-A-9-190628, JP-A-10-21 In JP-A-89-918 and the like, two types of binders having a high molecular weight and a lower molecular weight are mixed to achieve both film characteristics and developing characteristics.

On the other hand, the unsaturated compound plays a role of forming a crosslinked structure upon exposure and insolubilizing the film in an alkaline developer to form a pattern. For example, in Japanese Patent Application Laid-Open Nos. Hei 3-2504 and No. 62-287240, compounds having a carboxyl group and an acryloyl group in one molecule are used in combination. Together with the above role, it promotes reduction of development and photocurability. This is a compound with a molecular weight of less than 2000, which is obtained by simply adding monoanhydride to an epoxy resin and an acrylic acid reactant.To increase the molecular weight, only Novolac type epoxy resin is used. Carbon-carbon bond, and ether bond by self-condensation of epoxy resin. Furthermore, there are examples where this component can achieve the task of DFR conversion. Ethylene dalycol chains and Z or propylene glycol chains in various molecules Reports using a combination of polyfunctional acrylates and urethane acrylates, for example, Japanese Patent Application Laid-Open Nos. Hei 7-1991-153, Japanese Patent Application Laid-Open No. 9-190628, Japanese Patent Application Laid-Open No. 2-2 DFR can be used in Japanese Patent Application Laid-Open No. 697172, Japanese Patent Application Laid-Open No. 2-33253, Japanese Patent Application Laid-Open No. 11271744, Japanese Patent Application Laid-Open No. Flexibility, followability during lamination, adhesion to the substrate, and tending strength. Also, Japanese Patent Application Laid-Open No. 1-219734 discloses a polyfunctional acrylate having an acryloyl group in a dipentaerythr skeleton via a force prolacton chain (for example, Pharmaceutical DPCA-60, DPCA-120 etc.) can reduce the DFR tackiness without reducing the cross-linking property during exposure. However, in each case, these unsaturated compounds are low-molecular-weight compounds having a molecular weight of 2000 or less, and play a role of a plasticizer of a thermoplastic organic polymer binder as a main component, thereby improving the flexibility of DFR. Is what it is.

In addition, various physical properties are also adjusted by the mixing ratio of the thermoplastic organic polymer binder and the unsaturated compound. For example, in order to improve the cold flow, it is only necessary to increase the mixing ratio of the binder. However, cut chips are more likely to be generated, and the ability to follow the substrate is reduced. In order to prevent the occurrence of cut chips, the mixing ratio of the binder may be reduced. However, this causes a delay in development time due to cold flow, a decrease in the acid value of the coating film, and poor development.

More recently, high-density DFRs have been required as finer patterning of printed circuit boards has progressed. In addition, if the resist image formed on the fin is not adhered to by the pressure of the spray or the like in the developing or etching process, the wire is broken and leads to a failure. For this purpose, it is required that the resist images have good fine line adhesion. Also, to improve productivity It is required that the developing time and the peeling time be fast.

The photopolymerizable layer described above is peeled off after use as a resist.However, unlike these, the photopolymerizable layer is used as a permanent protective film by utilizing the physical properties of the cured film. There are also reports of the body. For example, there has been proposed a use in which a photopolymerizable layer is provided with heat resistance after curing and used as a solder resist. For example, in Japanese Patent Application Laid-Open Nos. HEI 3-11211-54 and H08-2888645, an acid anhydride adduct of a novolac-type epoxy compound and an acrylic acid reactant is used to form an acid anhydride. There is a proposal to use it as an imageable resin and make it a DFR. Since this resin also has a low molecular weight and is connected by a cresol novolak type methylene group, it is doubtful whether DFR is possible. In the former, there is no description about DFR in the examples. Recently, multilayering has been promoted as a further high-density mounting substrate, and the correlated insulating film or the passivation film constituting the wiring substrate on which this is mounted has heat resistance. Low dielectric constant, low water absorption, low coefficient of thermal expansion, high adhesion, and good chemical resistance are required. Furthermore, recently, in order to simplify the process of forming a via hole for conducting the multilayered upper and lower electrode wirings, the material itself has been developed so that the via hole can be formed by a process similar to the photo resist. It is preferred to have photosensitivity.

At present, polyimide resin (for example, JP-A-5-165217), organic silicon resin (for example, JP-A-3-43435) are used as interlayer insulating film materials having these characteristics. No. 5, JP-A-7-22508), benzocyclobutene resin (for example, Japanese Patent Publication No. 7-19773), heat-resistant epoxyacrylate resin (for example, No. 1 214141) has been proposed. Both polyimide resin and organosilicon resin have difficulty in forming high-precision and fine via-holes, so there is a limit to high density, and the curing temperature is more than 300 ° C. And high temperature, subject to the restrictions of the substrate. In addition, examples in which these are converted to DFR can only be found in polyimide resins, which are also in the state of polyamic acid, which is a polyimide precursor, and the polymer main chain is composed of amide bonds. Have been.

In addition, many acid-adducts of heat-resistant epoxy acrylate resins have been proposed as photosensitive resins capable of being fully developed (Japanese Unexamined Patent Publication No. Hei 4-340695, Japanese Unexamined Patent Publication No. JP-A-6363311, JP-A-8-288645, etc.). In each case, the connection is through a low molecular weight or cresol novolac type methylene group, and the DFR conversion is exemplified only in Japanese Patent Application Laid-Open No. Hei 8-28645, which also shows the possibility of DFR. Is the challenge. PCTZ JP 93/050536, JP-A-5-146132 and JP-A-8-1463111 disclose epoxyacrylate and acid diacid. An adduct with an anhydride is exemplified, but there is no description of DFR conversion and no description of its DFR properties.

On the other hand, a similar resin is used as a varnish for a display and applied to a glass substrate by spin coating (for example, see Japanese Patent Application Laid-Open No. Hei 4-34095, PCTZ JP 93/0). No. 053336). As the size of the display increases, the load on the spin coating device also increases, and coating uniformity has become an issue. For example, Japanese Patent Application Laid-Open No. 5-173320, Fujikura et al. (IDW98, Proceedings of the 5th IDW, 315H) have proposed a photosensitive resin multilayer laminate for the production of color filters. In addition, conventional spacers made of silica or spherical resin are also placed on one pixel, but a photosensitive resin or color resist is laminated on the black matrix to form a columnar spacer. A technology has been reported that achieves high contrast of liquid crystal displays by forming a sensor using photolithography (see SID International Symposium, Digest of Technical Papers, Vol. 27, 1996, pages 600 and 603, IDW98, Proceedings of the 5th IDW, 339 H). In order to keep the cell gap constant, it is necessary to form a 20 μm prism with a film thickness accuracy of 5 μιη ± 0.2 / im, regardless of the unevenness of the color-fetter base. For large substrates, there is a need for forming means that can replace spin coating of ceramics.

In view of the above, the present invention uses a vinyl copolymer as a conventional DFR to prevent cold flow by increasing its molecular weight, to improve film flexibility and strength, and to reduce lamination by reducing the molecular weight. It is an object of the present invention to provide a photopolymerizable laminate that solves the problem of achieving contradictory characteristics such as the ability to follow the substrate at the time and the good developability. Further, the present invention provides a register, an image forming material, and the like having a higher resolution than those of the related art. Furthermore, an object of the present invention is to provide a high-density, high-performance semiconductor device or display device because the cured product is excellent in heat resistance and the like.

(Disclosure of the Invention)

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a polyester-based copolymer having a completely different bonding system from the main chain formed by carbon-carbon bonds found in conventional vinyl-based copolymers. This problem has been solved by using a photopolymerizable layer in which is used as a binder.

That is, the present invention provides a photopolymerizable laminate having a photopolymerizable layer and a support layer, wherein the photopolymerizable layer is

(A) A carboxyl group-containing copolymer obtained by reacting a diol compound with an acid dianhydride, having a weight average molecular weight of at least 3,000 and less than 40,000 and an acid value of 500 To 100 parts by weight of resin, which is ~ 200 mgKOH / g,

(B) unsaturated compound containing two or more photopolymerizable ethylenic groups in one molecule 5 to 180 parts by weight, and

(C) 0.1 to 15% by weight of a photopolymerization initiator based on the total amount of the components (A) and (B);

And a photopolymerizable laminate.

Further, the present invention is a semiconductor device or a liquid crystal device, wherein the photopolymerizable laminate is laminated, and a cured film thereof is formed as a permanent film.

In the present invention, the diol compound to be reacted with an acid dianhydride to obtain a carboxyl group-containing copolymer has two hydroxyl groups in the molecule and two diols in the acid dianhydride from the viewpoint of increasing the molecular weight during the polymerization reaction. Those having the same reactivity with two acid anhydride groups, for example, those having a symmetric molecular structure are preferred.

Preferred specific examples of this diol compound include ethylene diol, diethylene glycol, polyethylene glycol, propylene glycol, hydrogenated bisphenol A, and bis (4-hydroxyphenyl) ketone. Tonone, bis (4-hydroxyphenynole) sunorehon, 2,2-bis (4-hydroxyphenynole) prono ,. Bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) hexafluoropronone, 9,9-bis (4-hydroxyphenyl) fluorene, bis (4 -Hydroxyphenyl) dimethylsilane, 4,4'-biphenol, or an addition compound of various diglycidyl ethers derived from these diol compounds with (meth) acrylic acid, alicyclic epoxy and ( Meta) Adducts with acrylic acid and adducts of the above-mentioned bisphenols with ethylene oxide or propylene oxide can be further exemplified. In particular, the acrylic acid adduct has a polymerizable unsaturated group and an alkali-soluble carboxyl group in the same molecule after the reaction with the acid dianhydride, and is therefore preferable for improving the exposure sensitivity and increasing the resolution. In particular, preferred diol compounds include: There is a compound represented by the formula (1)

(However, R i R s independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The compound represented by the above formula (1) usually contains an oligomer having η = 1 to 10 as shown in the formula (2) due to its synthesis method. In the present invention, the compound represented by the formula (1) The main component is the 0 component. (Mainly means that in the analysis using gel permeation chromatography, the η = 0 component should be 60% or more in the area ratio of the mouth matogram with the RI detector.) ).

Examples of the acid dianhydride used for the reaction with the diol compound ′ in the present invention include pyromellitic anhydride, benzophenonetetracarboxylic acid, and the like. Dianhydride, biphenylenolete tricarboxylic dianhydride, biphenylenoleatenoletetracarboxylic dianhydride, diphenylsulfone tetracarboxylic dianhydride, ethylene glycol monolevis trimethylate And methynolecyclohexene dicarboxylic anhydride. The acid dianhydride in the present invention includes carboxylic acid derivatives having the same effect, that is, carboxylic acid esters and acid halides.

In the copolymer containing a hydroxyl group, the acid dianhydride is 100 moles based on the diol compound. /. It is synthesized with a reaction charge ratio of less than. When the charge ratio of the acid dianhydride is 100 mol% or more, it is not easy to control the molecular weight of the obtained copolymer, and the photopolymerizable layer composition prepared from the obtained copolymer is difficult to control. Lack of storage stability. In order to obtain the desired weight average molecular weight of the copolymer having a desired weight average molecular weight of 30000 or more, the charge ratio of the acid dianhydride is preferably 5 ° mol to the diol compound in order to satisfy the desired DFR characteristics. % more than 9 5 mol% or less, good Ri favored properly 5 5 mole ^_0/0 more than 8 5 mol ⁰ /. It is as follows. Therefore, the unreacted diol compound and the compound in which one hydroxy group has reacted coexist with the carboxyl group-containing copolymer, but these are usually separated without separation in the photopolymerizable layer. used. The content of the unreacted diol compound is less than 30% by area in the GPC analysis described later.

The weight average molecular weight of the above-mentioned carboxyl group-containing copolymer is not less than 3,000 and less than 40,000. The molecular weight is determined as polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent. If the weight-average molecular weight exceeds 40,000, developability and resolution decrease, and if it is less than 3,000, the viscosity of the photopolymerizable layer decreases, so that cold flow is likely to occur and the cut-chip property deteriorates. I do. This best The molecular weight range is lower than that of the conventional vinyl copolymer, and it is considered that the resin of the present invention is based on a polyester / polyester resin.

The carboxyl group-containing copolymer has an acid value of 50 to 200 mgKOH / g, preferably 70 to 170 mgKOH / g. The acid value is expressed by the number of milligrams of the hydration power required to neutralize 1 g of resin. The individual acid value of the carboxyl group-containing copolymer differs depending on the polymer end, but the difference decreases with an increase in the degree of polymerization. Further, since the copolymer is obtained as a mixture containing the unreacted diol as described above, the measured acid value of the mixture may be approximated to the acid value of the carboxyl group-containing copolymer. When the acid value is less than 50 mgKOH / g, the development time is prolonged, and when it exceeds 200 mgKOH / g, the fine pattern is easily peeled off during development.

The carboxyl group-containing copolymer used in the present invention has good resolution and high-speed developability even when used alone, but has a weight average molecular weight of 3,000 to 7,000 and 7,000. , 000 to 400, 000, a more rapid development process is possible.

The carboxyl group-containing copolymer used in the present invention has a good alcoholic developability and a good copolymer despite its low molecular weight and acid value as compared with the conventional biel copolymer-based alkaline developable binder. It is possible to obtain a flexible film with no flow. The reason for this is that since the main chain of this copolymer is composed of ester bonds, it is a flexible film that has a lower degree of polymerization but has no cold flow as compared with the Bull copolymer. The DFR has unprecedented characteristics, in that it has a relatively low molecular weight, enabling rapid development.

The component (B) of the present invention comprises a photopolymerizable ethylenic group, preferably a terminal ethylene group. An unsaturated compound containing two or more lenic groups in one molecule, cross-links by light irradiation together with a photopolymerization initiator described below, and insolubilizes the photopolymerizable layer in an alkaline developer. I do. As such unsaturated compounds, known compounds that have been used in DFR can be used. Specific examples include those obtained by combining a polyhydric alcohol and a monounsaturated carboxylic acid, such as diethylene glycol (meth) acrylate (diata acrylate or dimethacrylate). Triglycerol glycol (meta) acrylate, tetraethylene glycol (meta) atalylate, trimethylolpropane (meta) acrylate Rate, trimethylol prono ,. Nji

(Meta) acrylate, trimethylolpropane tri (meta) acrylate, 1,3-pronondiol (meta) acrylate, 1,3-butanediol

(Meta) ata rerate, pentaerythritol tonolette (meta) atarelate, pentaerythritol tetra (meta) atarelate, dipentaerythritol

-Lehexa (meta) acrylate, dipentaerythritol pentapenta (meta) acrylate, DPCA manufactured by Nippon Kayaku Co., Ltd.-20, DPCA-30, DPCA-60, DPCA- The dipentaerythol derivative having an acryloyl group, such as that shown in Fig. 120, 2,2-bis (4-attalioxy xydiethoxyphenyl) prononone, 2,2-bis (4-methacryloxypentaene) Mixtures of toxicone, prononone, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane (Shin-Nakamura Chemical Co., Ltd., trade name: BPE-500), and glycyl group-containing compounds Which are obtained by adding α, monounsaturated carboxylic acid to, for example, trimethylolpropane triglycidinoleether tri (meta) acrylate, bisphenol monocyclidyl ether di (meta) Ata Rate, diglycidyl Shijirue having a fluorene ring - Accession acrylic acid adduct of ether [manufactured by Nippon Steel Chemical Co., Ltd. trade name: ASF400] etc. In illustrate Monkey

The unsaturated compound (B) is used in an amount of 25 to 180 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the carboxyl group-containing copolymer resin as a binder. . If the amount is less than 25 parts by weight, fine patterns are likely to flow during alkaline development, and the plating liquid resistance is poor. If the amount exceeds 180 parts by weight, cold flow during storage of DFR tends to occur, and the adhesion between the cured film and the substrate is poor.

Examples of the photopolymerization initiator (C) that can be used in the present invention include known initiators that are activated by various actinic rays, for example, ultraviolet rays, and start polymerization. Examples of such photopolymerization initiators include acetophenone, 2,2'-diethoxysetphenone, p-dimethylacetophenone, and p-tert-butylacetophenone. Acetophenones, benzophenones, 2-cyclobenzophenones, ρ, ρ, one bisdimethinorea minobenzophenone, 3,3,4,4,1 t La (tert-butyl phenol) Benzoin ethers, such as 2-methyl-1- [4- (methylthio) phenyl] -12-monforinopropanone-1,1,2-benzyl-2-dimethylamino-1- (4 —Mono Α-Aminoalkylphenones such as folinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoinole) phenylphosphine-oxide and glycines such as Ν-phenyldaricin , 2,4-Trichloromethyl-1- (pipyronyl) -16-triazine, 2,4-Trichloromethinole-1 (4,1-methoxytolyl) -16-Triazine And triazines such as azine.

The amount of the photopolymerization initiator (C) contained in the photopolymerizable layer of the present invention depends on the amount of the component (Α) And 0.1 to 15% by weight based on the total amount of component (B). When the amount of the photopolymerization initiator is less than 0.1% by weight, the sensitivity of the exposed portion is not sufficient, and the weight is 15% by weight. /. If used in excess of this, there is no effect on improving sensitivity, absorption of actinic light increases, curing at the bottom of the photopolymerizable layer becomes insufficient, and the pattern shape after development becomes an undesired tape.

Further, when the diol compound which is a raw material component of the carboxyl group-containing copolymer in the present invention has two or more polymerizable unsaturated groups in one molecule, a highly sensitive photopolymerizable layer can be obtained. In other words, the carboxyl group containing carboxyl group and the unsaturated group forming a crosslinked structure by light irradiation coexist in the carboxyl group-containing copolymer, and a large amount of unsaturated groups in one molecule by copolymerization. Since the group is introduced, it is possible to form a highly sensitive photopolymerizable layer that is insolubilized even with a small amount of light irradiation. This is because the main chain structure is different from that of a conventional cresol novolac epoxy acrylate acid monoanhydride adduct (for example, Japanese Patent Application Laid-Open No. 8-28864), and It is a polymer having a weight-average molecular weight of 3,000 or more, which is sufficient to have a polymer. Compounds that are both the component (A) and the component (B) are counted as the component (A).

The photopolymerizable layer containing the above (A) to (C) as essential components is capable of forming tape-shaped patterns with excellent resolution that is not available in conventional DFR, and is a high-density, high-definition device. I will provide a.

The carboxyl group-containing copolymer of the present invention can be prepared, for example, by reacting the diol compound and the acid dianhydride in a solvent having a boiling point of 100 ° C. or higher in the presence of a known catalyst at 60 to 130 ° C. It is obtained as a resin solution by heating at C for 2 to 20 hours. It is suitable that the reaction solvent has no hydroxyl group and has a boiling point higher than the reaction temperature, for example, ethynorecello-solozoleviacetate, propylene glycol cornolemonomethionolate. J / 114 Ether, ester, and ketone solvents such as ether acetate, diglyme, ethyl carbitol acetate, silk hexanone, and diisobutyl ketone are preferably used. The reaction may also be used in ◦. 0 0 range from 1 to 1 weight ^_0/0 catalyst purposes against the diol of compound that promotes. As an example of the catalyst, a known catalyst such as tetraethylammonium bromide can be used.

For the purpose of ensuring the thermal stability of the polymerizable unsaturated group, a polymerization inhibitor such as di-t-butylhydroxytoluene may be added in a range of 0.1% by weight or less based on the diol compound. ,.

Carboxyl group-containing copolymer were charged acid dianhydride in the synthesis is carried out in 1 0 less than 0 mole ^_0/0 of the charge Jio Le compounds. If the charge is 100 mol% or more, it is not easy to control the molecular weight of the obtained copolymer, and the photopolymerizable layer composition prepared from the obtained copolymer lacks storage stability. Further, the diol compound and the acid dianhydride used in the copolymerization are not limited to one kind, and a copolymer may be used by using two or more kinds. Furthermore, an acid monoanhydride or a monofunctional hydroxy compound may be used in combination for capping the terminal of the copolymer. Particularly, the polymer having a relatively low weight-average molecular weight of 3,000 to 7,0,0 is preferred. It is suitable for obtaining 100 copolymers. When acid monoanhydride is used for terminal blocking, the amount charged is 5 mol% or less of acid dianhydride, and the sum of 2 times mol of acid monoanhydride and the number of moles of acid dianhydride Should not exceed the number of moles of the diol compound. When used in the monofunctional human Doroki shea compound endcapping is 5 0 mole ⁰ / the charged amount of the diol compound. It is as follows. Known examples of such an acid monoanhydride are used, and examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, and methylcyclohexyldicarboxylic anhydride. In addition, monofunctional hydroxy compounds As the P / JPO / 01814 compound, a known compound such as a monofunctional epoxy acrylate can be used.

From the power of the above preparation, it is necessary to form a copolymer in order to obtain a weight average molecular weight of not less than 3,000, which is necessary for DFR to hardly cause cold flow and to have flexibility. The molecular weight of the repeating unit is preferably larger, more than 600, more preferably more than 700. Similarly, a diol containing an aromatic skeleton and / or an acid dianhydride is preferable as a composition which does not easily cause cold flow, and has a lower molecular weight than an aliphatic system. Rows can be prevented.

In view of the above, the preferred acid dianhydride is aromatic tetracarboxylic dianhydride. Preferred diols include aromatic bisphenols and their epoxides, adducts of propylene oxide, and more preferably (meta) aders of aromatic bisphenols to diglycidyl ethers. It is a acrylate adduct, that is, bishydroxypropyl (meta) acrylate. Specific examples are as described above.

The photopolymerizable layer of the present invention is formed by uniformly applying the photopolymerizable resin composition containing the above components (A) to (C) on a transparent support film and drying the solvent. Is done. This photopolymerizable resin composition contains an essential component and an organic solvent necessary for dissolving or uniformly dispersing an additive added as needed. The solid content in the composition is 10 to 70%. It is added so as to be% by weight. The concentration is arbitrarily selected depending on the coating method and the desired film thickness. Specific examples of the organic solvent used for this include propylene glycol monomethyl ether acetate, diglyme, ethyl acetate, butyl acetate, methyl ethyl ketone, etc., esters, ethers and ketones. It is preferably used and can easily dissolve or disperse solids, and must be sufficiently removed during the coating drying process. / 0 1 In addition, the photopolymerizable composition constituting the photopolymerizable layer includes a polymerization inhibitor for improving thermal stability and storage stability, coloring substances such as dyes and pigments, and Known substances such as a surfactant and a thermal crosslinking agent such as an epoxy resin or a melamine resin may be added according to the purpose and application. For example, an epoxy compound is effective as a means for improving the heat resistance, alkali resistance, and plating resistance of a cured product for interlayer insulating films, and an average particle size for coloring for one color filter. Add phthalocyanine blue (PB15: 6), phthalocyanine green (PG36), anthraquinone red pigment (PR177), etc., finely dispersed to a diameter of 0.3 μm or less.

The photopolymerizable resin composition containing the components (A) to (C) of the present invention may contain a solvent and the above-mentioned additives. The ingredients are at least 50% by weight, preferably 80% by weight, of the solid content (excluding pigments). / ₀ or more power, yo ,.

As described above, the essential components (A) to (C) and the additives are dissolved or uniformly dispersed in an organic solvent to prepare a photopolymerizable composition solution. This photopolymerizable composition solution is uniformly applied to a support film by a coater, dried by hot-air drying or the like, and then, if necessary, covered with a protective film and wound. The drying temperature is preferably 80 to 120 ° C in consideration of the thermal stability and productivity of the unsaturated compound. It is also desirable to raise the temperature in multiple stages to prevent skinning and foaming of the coating surface during drying. An organic solvent often remains in the dried photopolymerizable layer, but its content must be 15% by weight or less, preferably 1 °% by weight or less. The content here is 100% by weight of DFR after drying. The reduced weight as the absolute dry weight after drying again at 200 ° C for 30 minutes as / ₀ . / ₀ . If this exceeds 15% by weight, cold flow tends to occur. The thickness of the photopolymerizable layer after drying varies depending on the application, but is 1 to 10 µm for liquid crystal displays and 5 to 100 // m for circuit boards. Although the resolution is improved as the thickness of the photopolymerizable layer is smaller, the present photopolymerizable laminate can form a via and a fine line equivalent to the thickness of the photopolymerizable layer. For example, when the thickness is 30 / Π1, a via of 30 μπι and a line and space of 2 ぺ Aim can be formed. In 5 // ΙΏ, an isolated line and an isolated dot of 20 / i in can be formed.

As the support film for coating the photopolymerizable layer, a transparent film that transmits active light is desirable. Examples of such a support layer that transmits the active light include a well-known potile terephthalate frame, a polyacrylelem, a polypropylene film for optics, and a cellulose derivative film. The thickness of these films is generally 10 to 30 μm because the thinner the film, the more advantageous it is in terms of image forming properties and economy, and it is necessary to maintain strength.

In the photopolymerizable laminate, a protective film is laminated as necessary on the surface of the photopolymerizable layer which is not in contact with the support film, but the characteristics required for this protective film are different from those of the support film. In addition, the protective film has a sufficiently small adhesion to the photopolymerizable layer and can be easily peeled off. An example of such a film is a polyethylene film.

The production of a circuit board using the photopolymerizable laminate of the present invention, the production of a multi-chip module, and the production of a color filter and a spacer for a liquid crystal display are performed by known techniques. The process is briefly described below.

If there is a protective film, first peel off the protective film, then heat-press and laminate the photopolymerizable layer on the substrate surface using a hot roll laminator, etc., at a heating temperature of 70 to 120 ° C. The temperature is preferably 80 to 110 ° C. When the temperature is lower than 70 ° C, the adhesion to the substrate is poor. When the temperature exceeds 120 ° C, the photopolymerizable layer protrudes from the side edge, and the film thickness accuracy is impaired. This laminating property depends on the melt viscosity-temperature characteristics of the photopolymerizable layer. Good laminating properties can be obtained when the melt viscosity is between 100,000 and 10,000 Voids, and when the melt viscosity exceeds 100,000 Vois, it can be filled into fine irregularities on the underlayer and adherence to the substrate. If the size is less than 1,000, the photopolymerizable layer will protrude from the end face of the protective film during lamination. The photopolymerizability of the present invention provides such a viscosity characteristic in a temperature range suitable for the laminate. The melt viscosity referred to here is determined by peeling only the photopolymerizable layer from the obtained DFR, filling it in a lmm ci) cavity, and using a cavity rheometer (Flow Tester CFT500 manufactured by Shimadzu Corporation). It was measured with a load of 1 kg.

Next, if necessary, the support layer is peeled off, and image exposure is performed with active light through a mask. If there is a support film on the photopolymerizable layer, it is removed if necessary, and then the unexposed portions of the photopolymerizable layer are developed and removed using an aqueous alkali solution. As the aqueous alkali solution, an aqueous solution of sodium carbonate, potassium carbonate, sodium hydroxide, diethanolamine, tetramethylammonium hydroxide or the like is used. These alcohol developers are selected according to the characteristics of the photopolymerizable layer, but are generally used at a concentration of 0.05 to 3%, and can be used in combination with a surfactant. Next, when the substrate is a copper-clad circuit board, a metal image pattern is formed on the metal surface exposed by the development by using either a known etching method or a plating method. After that, depending on the application and the required performance, the photopolymerizable layer pattern is peeled off by a strong alkali solution, and is laminated in the same manner after heat curing while leaving a film, and used as a permanent protective film.

In particular, the photopolymerizable laminate of the present invention can be used when laminated on a substrate by laminating. Nevertheless, it has excellent high-resolution patterns and fine line adhesion, and can be suitably used for forming images and semiconductor circuits. Further, since the cured film retains high heat resistance and high adhesion to a substrate, it can be suitably used as a correlated insulating film, a color filter, a colored layer, a protective film, and a spacer material.

(Best mode for carrying out the invention)

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples, and Comparative Examples. The evaluations of the copolymer resins in the following synthesis examples are as follows unless otherwise specified.

[Solid Content] About 1 g of the obtained resin solution is impregnated with a glass filter W ₀ (g), weighed Wi (g), and heated at 160 ° C. for 2 hours, and then weighed. It was determined from W ₂ (g) by the following equation.

Solid content concentration (% by weight) = 100 X (W ₂ -W ₀ ) / (Wj-Wo)

[Acid value] The obtained resin solution is placed in a mixed solution of dioxane and ethanol in an equal volume, and titrated with an aqueous solution of 1 / 10N-KOH ethanol (50%) using phenolphthalein as an indicator. I asked.

[Molecular weight] The molecular weight was determined by gel permeation chromatography (GPC) equipped with an RI (refractive index) detector using tetrahydrofuran as a developing solvent. The molecular weight shown is the weight average molecular weight (Mw) in terms of polystyrene of the carboxyl group-containing copolymer portion excluding unreacted raw materials.

The abbreviations used in the synthesis examples are as follows.

FHPA: Equivalent reaction product of fluorene-type ethoxy resin and acrylic acid (Nippon Steel Chemical: ASF-400) BFHE: S (2-hydroxyethoxyphenyl) fluorene (Nippon Steel Chemical Co., Ltd.)

PHPA: 2,2-Hydroxyphenyl (2-hydroxyphenyl) equivalent reaction product of acrylic resin and acrylic acid

SHPA: phenyl sulphone type epho. Equivalent reaction product of xy resin and acrylic acid

PNOVA: Equivalent reaction product of acrylic acid with phenolic phenolic phenolic resin (Ephoxy, with an equivalent weight of 190 and having an average of 6 phenolic core residues in one molecule)

BPDA: Biphenyltetracarboxylic dianhydride

BZDA: benzophenone tetracarboxylic dianhydride

DSDA: diphenylsulfonetetracarboxylic anhydride

TPDA: pyromellitic anhydride

THPA: Tetrahydrophthalic anhydride

PGMEA: Pro-Pirendari Call Mono Methynoleate

TEABr: Tetraethylammonium Bromide

Synthesis example 1

In a 500 m4 four-necked flask with a reflux condenser, 75.0 g of bisphenol fluorene type epoxy resin (ESF-300, Nippon Steel Chemical Co., Ltd., epoxy equivalent: 25.7) was added. L-ethylbenzinoleammonium chloride 130 mg, tetraethylenolepenzinolenmolebromide 27 O mg, 2,6-diisobutyne norfenenole 29 mg and atalinole Acid 2.0 g and PGMEA 17EA g were charged, and the mixture was stirred and heated at 100 to 105 ° C for 16 hours while blowing dry air at a rate of 20 ml. Was. The obtained resin was further diluted with 79 g of PGMEA, and a pale yellow transparent dihydroxy resin having a solid concentration of 50% by weight was prepared. Pyracrylate resin solution (FHPA solution: acid value 1.28 mg KOH Zg in terms of solid content; An epoxy equivalent of 2130) was obtained. Synthesis Examples 2 to 8

300 g of the FHPA solution obtained in Synthesis Example 1 in a 300 m 1 four-necked flask with a reflux condenser and Og, and the proportions of acid dianhydride, PGME A and TEABr shown in Table 1. And stirred for 2 hours while heating at 120 to 125 ° C, and then for 8 hours with heating at 60 to 62 ° C to obtain a carboxyl group-containing copolymer resin solution A-1. ~ Α-7.

Table 1 shows the acid value (in terms of resin solid content) of the obtained resin solution and the result of GPC analysis (area% of carboxyl group-containing copolymer in the resin solution, weight average molecular weight).

Synthesis Examples 9 to 12

As a diol compound, BFHE, using 5 0 weight ⁰ / OPGMEA solution of PHP A or SHPA, viewed charged in the proportions shown dianhydride, the PGMEA and TEABr in Table 1 were performed in the same manner as in Synthesis Example 2, Carboxyl group-containing copolymer resin solutions A-8 to A-11 were obtained.

Synthesis Example 1 3

Using the FHPA solution obtained in Synthesis Example 1, THPA, PGMEA and TEABr were charged at the ratios shown in Table 1, and the same procedure as in Synthesis Example 2 was carried out to obtain a carboxyl group-containing copolymer resin solution a-1.

Synthesis Example 1 4

55.5 g of a phenol novolac-type epoxy resin having an epoxy equivalent of 190 and having an average of 6 phenolic core residues in one molecule and 21.6 g of acrylic acid were added to PGMEA7. Except for using 1 g, an acrylic acid adduct resin solution (PNOVA solution) was obtained in the same manner as in Synthesis Example 1. 96.0 g of this resin solution and 24.0 g of tetrahydrophthalenoic anhydride, propylene glycol monomer The reaction was carried out in the same manner as in Synthesis Example 2 except that the amount of tyl ether acetate was changed to 7.5 g, to obtain a resin solution a-2. Table 1 shows the charged amounts of each synthesis example, and Table 2 shows the analysis results of the obtained copolymer. [Table 1]

Synthetic diol compound Acid dianhydride or PGMEA TEABr Example No Combined (50% PGMEA solution) Acid anhydride

Village g village g village g quantity g

2 A- 1 FHPA 96.0 BPDA 14.4 0.16 0.15

3 A- 2 FHPA 96.0 BPDA 17.5 2.5 0.15

4 A- 3 FHPA 96.0 BPDA 12.8 0 0.15

5 A- 4 FHPA 96.0 BPDA 10.8 1.64 0

THPA 5.6

6 A-5 FHPA 96.0 BZDA 15.8 1.1 0.15

7 A- 6 FHPA 96.0 DSDA 17.5 2.3 0.15

8 A- 7 FHPA 96.0 TPDA 10.7 0 0.15

9 A- 8 BFHE 96.0 BPDA 20.2 8 0.2

1 0 A- 9 PHPA 96.0 BPDA 18.2 3 0.15

1 1 A-10 PHPA 96.0 TPDA 13.5 0 0.15

1 2 A-ll SHPA 96.0 BPDA 17.2 2.1 0.15

1 3 a- 1 FHPA 96.0 THPA 10.4 0 0.15

1 4 a- 2 PNOVA 96.0 THPA 24 10 0.15

[Table 2]

Example 1 19, Comparative Example 1 4

Using the carboxyl group-containing copolymer resin solution obtained in the above Synthesis Example, the unsaturated compounds, photopolymerization initiators, epoxy resins, and other additives shown in Table 3 were dissolved or dispersed in an organic solvent. A solution of the photopolymerizable resin composition was prepared. The solution was applied to a polyester film having a thickness of 25 μππ and a width of 600 mm using a die coater, and the resulting solution was subjected to 80 — 90 — 100 — It was dried with hot air in a continuous four-stage drying oven set at 120 ° C., respectively, to obtain a 30 μm-thick photopolymerizable layer having a residual solvent ratio shown in Table 3. A 60 / m-thick polyethylene protective film was laminated on the dried coating film, and the DF shown in Example 119 and Comparative Example 14 was used. R was manufactured (however, in Comparative Examples 3 and 4, the final stage of the drying furnace was set at 100 ° C.). The film properties of the obtained DFR were tested as follows. Table 3 shows the conditions and results.

Examples 1 to 19 showed good DFR characteristics, whereas Comparative Example 1 obtained good DFR characteristics because only the acid monoanhydride was used in the synthesis of component (A) and the molecular weight was low. I couldn't. In Comparative Example 2, since the resin (A) component is based on a phenol novolac epoxy acrylate that is brittle, the molecular weight is not increased by the acid dianhydride as in the present invention. There was a problem with the cut tip properties. Further, in Comparative Example 4, the residual solvent amount was high, and the cold flow characteristics were not good.

[Residual solvent ratio] Using an A4 size DFR, peel off the protective film and then press-bond it to a glass substrate G (g) heated to about 50 ° C, peel off the supporting film, and remove the supporting film. The substrate Di (g) was weighed. Subsequently, the glass substrate with a photopolymerizable layer was heated at 200 ° C. for 30 minutes, immediately weighed D ₂ (g), and the residual solvent ratio (%) was defined by the following equation.

Residual solvent ratio (%) = 10 Ox (D ₂ -G) / (Di_ G)

[Cold flow property 1] When the obtained DFR was stored in a rolled state at 5 ° C,

樹脂; No resin protrusion for more than 4 months

X: Resin oozes out in less than 4 months

[Cold flow property 2] Only the photopolymerizable layer was peeled off from the obtained DFR, and filled in a lmmφ kyary. Using a kyaryry rheometer (Shimadzu Co., Ltd. flow tester 1 CFT500) Measure melt viscosity with 1 kg load did. At this time,

〇; Flow starts above 50 ° C

X; Flow starts below 50 ° C

[Cutting property] DFR was cut from the polyester film support layer with a cutter knife.

〇； The cut surface is not cracked

X: The cut surface is cracked

[Flexibility] DFR with width of 2 O mm x length of 100 mm is peeled off from the polyethylene protective film, and then the photopolymerizable layer surface is microscopically examined when it is bent 90 degrees with the support film side inside. Observed. The evaluation was performed according to the following criteria.

〇; no cracks

X; cracks are seen

[Lamination and developability test on single-sided copper-clad laminate]

Using a hot-open laminator, the photopolymerizable layer is peeled off the DFR protective film on the copper surface of a copper-clad laminate (Esbanex manufactured by Nippon Steel Chemical Co., Ltd.) on which 18 m rolled copper foil is laminated. The lamination was performed at a roll temperature of 100 ° C and a transfer pressure of 3 kg fZ cm ² G at a transfer speed of 25 cm / min.

After the support film was peeled off, a quartz mask was adhered to the photopolymerizable layer and exposed to 300 mJ / cm ² using an ultra-high pressure mercury lamp (manufactured by Hitec Co., Ltd., illuminance: 1 lmj Z cm ² , I-line standard). Subsequently, it was developed for 90 to 120 seconds while penetrating in an aqueous solution of 1.2% tetramethylammonium hydroxide at 25 ° C to form an image pattern. The DFR was evaluated based on the following criteria, and the results are shown in Table 3.

From Examples 1 to 19, it was found that the present invention provides a DFR having high resolution and excellent fine line adhesion. On the other hand, in Comparative Examples 1 and 4, tackiness and fine line density were observed. There was a problem with the adhesion, and it was found that Comparative Example 3 was inferior in resolution.

[Tackiness] When a quartz mask is adhered to the photopolymerizable layer,

〇; The mask does not stick to the photopolymerizable layer

X: Mask sticks to photopolymerizable layer

[Resolution] The minimum line width (μπι) that can be obtained after exposure and development through a mask with a line and space width of 1: 1 and the minimum width that can be formed through a circular mask. The resolution was defined as the via diameter (μπι).

[Fine line adhesion] One cured resist line obtained after exposure using a chrome photomask with exposure areas of 5 to 100 μm arranged at 300 μm intervals and development The minimum line width (im) with no flow or chipping was regarded as fine wire adhesion and evaluated according to the following criteria.

30 μm or less ◎

4 0 / ί Πΐ〜 5 0 / πι

More than 5 0 μιη

[Substrate followability test]

180, 100, 80, 60, 40 / xm LZS on the copper surface of a copper-clad laminate (Espanex manufactured by Nippon Steel Chemical Co., Ltd.) Was previously formed. Then, in the direction parallel to the line formed on this substrate, the photopolymerizable layer was peeled off using a hot roll laminator while the protective film of the DFR was peeled off, with a port temperature of 100 ° C and a transfer pressure of 3 kg Z cm ² ■ G, Laminated at a transfer speed of 25 cm / min. Subsequently, after exposing at 300 mJ / cm ² from above the polyester supporting finolem, the supporting film was peeled off. The following evaluation was performed on the obtained film using a polarizing microscope and a surface roughness meter (Thermcom 57 OA manufactured by Tokyo Seiki Co., Ltd.). [Background followability]

The resulting film was observed with a polarizing microscope to confirm that air bubbles remained.

No air bubbles can be seen '· · 〇

Air bubbles are seen · · · X

[Surface flatness] Using a surface roughness meter, the undulation θ (μm) of the photopolymerizable layer between the upper part of the copper foil pattern and the groove was measured, and the surface flatness was determined by the following equation.

Flatness (%) = 1 0 0 — Ι 0 0χ (θ / 18)

Flatness 95% or more '· ■ ◎

Flatness 90% or more and less than 95% ...

Flatness 90. /. Less · · · X

[Table 3]

1814

* 1) Development was performed at 25 ° C in a 0.24% TMAH aqueous solution. Others were developed in a 1.2% TMAH aqueous solution at 2'5 ° C.

* 2) Transfer failure occurred with the photopolymer layer remaining on the-part support film side.

* 3) During lamination, the photopolymer layer often protruded from the end face of the supporting film.

* 4) Measurement not possible

* 5) Not measured

DPHA; Y'Pentaerys ¹ J Thorhexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: trade name KAYARAD DPHA) DPCA-60 and DPCA-120; (Nippon Kayaku Co., Ltd .: trade name KAYARAD DPCA) Nxaerythritol hexaacrylate cuff. Mouth rataton metamorphosis

[(CH ₂ O-) 3C-CH ₂ -O-CH2-C (CH ₂ O-) ₃ ]-[(CO-C ₅ Hi0-O) m-CO-CH = CH ₂ ] a

DPCA-60: m = l, a = 6

DPCA-120: m = 2, a = 6

Same as above (manufactured by Nippon Kayaku Co., Ltd .: Trade name KAYARAD DPCA-120)

YX-4000H] a; Tetramethylphenyl phenyl-type ethoxy. Xy resin (Yukaka Shell Co., Ltd .: trade name YX4000H ゝ ethoxy. Xy equivalent 170)

EOCN; Creso "Renoho" rack type Kishijutsuki (Nippon Kayaku Co., Ltd., trade name EOCN-1020-80, Eho. Kishimoto m 200)

907; 2-methyl-1- [4- (methylthio) phenyl] -2-monofurinoff. Loha. -1 (Ciba Specialty Chemicals Co. Ltd .: trade name IRGACUR 907)

EAB-F; 4,4'-Succilamiha'nso, 'Fuenone (Hodogaya Chemical Industry Co., Ltd .: trade name EAB-FF)

S-501; made by Chisso Corporation: Brand name Site Laces S-510

FC430; manufactured by Sumitomo SL: Company name: FLORA-FC FC-430

IrganoxlOlO; Antioxidant (Ciba Specialty Chemicals Co. Ltd .: IRGACUR 907) PGMEA; . Pyrenk "Ricol monomethyl ether acetate (Kyowa Hakko Kogyo)

a-3; meta click Li Rusanme chill 4 7 wt ^_0/0, 2 3 wt meta data Li Le acid ^_0/0, styrene 3 0 wt% of 3 Mechiruechiruke tons solution of terpolymer (solids 32% by weight, weight-average molecular weight 4500)

a-4: styrene 55 weight ⁰ /. , § click acrylic acid 3 5 weight ^_0/0, a - methylstyrene 1 0% by weight of terpolymer (weight average molecular weight 1 5 0 0 0) Example 2 0

DFR was laminated on the copper-clad laminate (S-Vanex) in the same manner as in the above example, and exposed and developed in the same manner to form a 50 μτη via hole. After degreasing, washing with water, soft etching, neutralization, and washing with water, gold plating was performed on the via holes. Thereafter, the photopolymerizable layer was peeled off, and no opacity was observed.

As described above, it was found that the photopolymerizable laminate of the present invention exhibited good adhesion despite being transferred by a hot-laminator.

Example 21 to 24

The resin compositions shown in Table 4 were prepared using the carboxyl group-containing copolymer resin solutions obtained in Synthesis Examples 2 and 5. The resulting composition was applied to a polyester finolem having a thickness of 16 μπα and a width of 600 mm using a blade coater, and the temperature was set at 80 ° -90 ° -95 ° -100 ° C, respectively. It was dried with hot air in a continuous four-stage drying oven to obtain a photopolymerizable layer having a residual solvent ratio and a film thickness shown in Table 5. A 60 m-thick polyethylene protective film was laminated on the dried coating film to produce the following DFR for display material.

Example 2 1 Transparent film with a thickness of 5 μππ for LCD spacer applications Example 2 2 LCD protective film · Viewing angle improving structural material Use 2 μm thick transparent film Example 2 3 Color filter-1.3 m thick blue colored film

Example 2 4 Flux matrix Thickness 1.1 // m Black film

From the DFR, each photopolymerizability was thermocompression-bonded on a glass substrate at 100 ° C. using a hot roll laminator. After peeling off the poly ester support film, 3 0 O mJZ cm ² exposed through a quartz mask (bra click is 5 0 0 m J cm ^2), thereby forming a pattern in Table described developing conditions. Further, postbaking was performed in a hot blast stove at 220 ° C for 30 minutes. Table 5 shows the evaluation results. The evaluation method is as described above, except for the following items.

[Heat transfer property] When the photopolymerizable layer is transferred to the glass substrate without remaining on the polyester support film when the polyester support film is peeled off after exposure with hot roll laminating, X.

[Resolution] The resolution was defined as the minimum line width (xm) at which the obtained image could be separated after exposure and development through a mask with a line and space width of 1: 1.

[Fine line adhesion] A single cured resist line obtained after exposure using a chrome photomask in which exposure lines of 5 to 100 μm and square dots are arranged at intervals of 300 m, and developed. However, the smallest line width (tm) or square dot with no flow or chipping was used for close adhesion.

[Pattern shape] The following pattern shapes suitable for various DFR applications are indicated as “〇” when the taper is forward tapered, and “X” when the shape is reverse tapered. The measurement was performed using a scanning electron microscope.

[Surface hardness] A pencil hardness test was performed on the coating film after the boss beta according to the JIS standard. The pencil hardness at which no scratch was observed on the surface was defined as the surface hardness.

[Adhesion] Cross force to make at least 100 grids on the cured film Then, a peeling test was performed using cellophane tape, and the state of the cross-cut peeling was visually evaluated. The ranking of the evaluation is as follows.

：: No peeling is observed

X: Peeling is recognized even a little

[Chemical resistance] Immediately after the cured film was immersed in the following chemical solutions, a crosscut was immediately made to conduct an adhesion test. The judgment was based on the adhesion test.

I Sopro Piranore Co .: 2 3. C, 30 minutes

N-methyl-1-pyrrolidone (NMP): 40 ° C, 10 minutes

5wt%-NaOH aqueous solution: 23 ° C, 30 minutes

5wt%-HCl aqueous solution: 23 ° C, 30 minutes

[Transparency, chromaticity, light blocking ratio (OD value)] Using a chromaticity meter (Tokyo Denshoku Co., color analyzer TC-1 800MK2), the transmittance of the transparent cured film at 400 nm was measured. Was determined.

Transmittance 90% or more '■ · 〇

Transmittance 90% or less' X

Similarly, the chromaticity of the blue-colored film was measured. The light blocking ratio of the black coating film was measured using an optical densitometer (DM560, manufactured by Dainippon Screen Co., Ltd.).

In Example 21, it was found that a dot of 2 ° / Xm required for the liquid crystal spacer was formed in a regular taper and the top was flat. The adhesion was also good.

In Example 22, the transparency and adhesion required for the protective film agent were good, and the 1 O / m line required for the structural material for improving the viewing angle could be formed. In Examples 23 and 24, the transferability was good, and the cured film was found to have satisfactory optical properties and chemical resistance as a color filter, and also had excellent resolution.

[Table 4]

TAZ 1 10: 2, 4-Triclomethyl- (4-methoxystyryl) 16-Triacy

Pigment menthol 15: 6 fine dispersion in PGMEA solvent, 15: 6, Mikuni Dyestuffs Co., Ltd. Flak pigment dispersion; Dispersion of force-Honfurac in PGMEA solvent, Made by Okuni Pigment [Table 5]

(Industrial applicability)

According to the present invention, since the main component of the photopolymerizable layer is a carboxyl group-containing polymer formed by an ester bond, the film has low molecular weight and low flexibility compared to conventional bullet copolymers. It has anti-flow performance and good developability. A novel photopolymerizable laminate capable of forming an unprecedented high-resolution buttery-battery-battery pattern is provided. Furthermore, not only a high-resolution resist but also a permanent protective film utilizing its hardened film characteristics is effective as a material contributing to higher performance of semiconductor devices and display devices. The photopolymerizable laminate of the present invention includes a solder resist, a plating resist, an etching resist for forming a circuit board, an insulating film for multilayering a wiring board on which a semiconductor element is mounted, a photosensitive adhesive, and the like. It can be used for It can also be used as a material for semiconductor devices and liquid crystal devices.

Claims

The scope of the claims

(1) In a photopolymerizable laminate having a photopolymerizable layer and a support layer, the photopolymerizable layer is

(A) A carboxyl group-containing copolymer obtained by reacting a diol compound with an acid dianhydride, having a weight average molecular weight of not less than 3,000, less than 40,000, and an acid value of 5 With respect to 100 parts by weight of a resin that is 0 to 200 mg KOH / g,

(B) 25 to 180 parts by weight of an unsaturated compound containing two or more photopolymerizable ethylenic groups in the molecule, and

A photopolymerizable laminate comprising (C) a photopolymerization initiator in an amount of 0.1 to 15% by weight based on the total amount of the components (A) and (B).

(2) The photopolymerizable laminate according to claim 1, wherein the diol compound has two or more polymerizable unsaturated groups in one molecule.

(3) The photopolymerizable laminate according to claim 1, wherein the repeating unit of the copolymer has a molecular weight of 600 or more.

(4) The photopolymerizable laminate according to claim 1, wherein the diol compound is aromatic dipropyl hydroxyacrylate and the acid dianhydride is an aromatic dianhydride.

(5) The photopolymerizable laminate according to claim 1, wherein the diol compound is a fluorene bisphenol epoxy acrylate represented by the following formula (1).

(1)

(However, R i R s independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(6) A semiconductor device, comprising: laminating the photopolymerizable laminate according to any one of claims 1 to 5; and forming the cured film as a permanent film.

(7) A liquid crystal device comprising the photopolymerizable laminate according to any one of claims 1 to 5, and a cured film formed as a permanent film.