JP2002148792A - Method for manufacturing resin layered body and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a resin layered body by which production of air bubbles during transfer by a lamination method can be suppressed and a resin layered body with no defect, high accuracy and low cost can be fast and stably formed by laminating. SOLUTION: In the method for manufacturing a resin layered body includes processes of removing a protective film from a photosensitive resin material having a photosensitive resin layer and the protective film on a supporting body, adhering the photosensitive resin layer of the photosensitive resin material to the surface of a substrate to laminate, and peeling the supporting body after lamination to transfer the photosensitive resin layer onto the substrate, at least the surface subjected to the transfer process of the substrate is controlled to have <=35 dyne/cm surface free energy in the polar component in the laminating (transferring) process. The dispersion component of the surface free energy is preferably <=40 dyne/cm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resin laminate and a color filter, and more particularly, to a resin laminate suitable for producing a color filter, a spacer and an alignment control structure used for a liquid crystal display device. And a color filter obtained by the method.

[0002]

2. Description of the Related Art As a resin laminate used for a liquid crystal display device, there are a color filter, a spacer, an alignment controlling structure and the like. Generally, a liquid crystal display device for displaying a color image has a configuration in which a color filter is provided on one surface of two transparent substrates provided in the liquid crystal display device. The color filter has a configuration in which colored pixels composed of a large number of colored layers are arranged on both sides of a transparent substrate in a vertical and horizontal direction with a minute gap therebetween. A large number of colored pixels are usually colored in any one of three colors of R (red), G (green), and B (blue), and each colored pixel of RGB is arranged in combination in a fixed pattern.

[0003] Various methods are known as a method for producing the above resin laminate such as a color filter.
2. Description of the Related Art A transfer method (laminate method) using a photosensitive resin sheet (photosensitive resin material) has attracted attention because a high-precision color filter or the like can be easily manufactured. For example, in a method of manufacturing a color filter, in a transfer method using this photosensitive resin sheet, first, a photosensitive colored resin layer (photosensitive resin layer) containing a colored material (pigment or dye) of a predetermined color and a photosensitive resin is used. ) Is provided on a flexible support sheet by a predetermined number of photosensitive resin sheets (usually,
R, G, B). Next, one of the three types of photosensitive resin sheets was placed and overlapped so that the surface of the photosensitive resin layer was opposed to the surface of a transparent substrate (such as a glass plate) to be transferred. A color filter can be prepared by laminating the support sheet on a substrate by heating while passing through a heating roll and laminating the support sheet, and transferring the photosensitive coloring layer onto a transparent substrate.

Subsequently, in this state, the surface of the photosensitive resin layer is irradiated with light through a sheet-shaped photomask having a pixel pattern portion opened to expose the photosensitive resin layer in a pattern and further developed. Thus, a colored pixel pattern of one color is formed on the transparent substrate. By using a photosensitive resin sheet having a photosensitive resin layer of another color on the surface of the substrate on which the colored pixel pattern is formed, the same operation is performed to sequentially perform transfer, exposure, and development, so that multicolor coloring is performed. A pixel pattern can be formed. Then, in order to improve the color separation between the multicolored pixels such as RGB, a photosensitive black resin is buried between the pixels formed with gaps, and a so-called black matrix is generally formed.

[0005] In recent years, demand for color filters and the like has been increasing more and more, and under such circumstances, improvements in various performances of the color filters and the like and lower prices have been demanded. Therefore, it is strongly desired to establish a technique for manufacturing a high-precision color filter or the like at low cost. One method of manufacturing a resin laminate such as a color filter at low cost is to reduce the time required for manufacturing. In addition, with the development of devices having a new layer structure such as a COA (color filter on array) and a plastic cell, a laminate having a versatile structure has been required, and various types of manufacturing methods using a transfer method have been required. In many cases, lamination is performed on a substrate (SiN film, plastic material, etc.).

The method of manufacturing a resin laminate using the above-described transfer method is advantageous for manufacturing a high-precision color filter or the like, but a photosensitive resin sheet (photosensitive resin material) is bonded on a transparent substrate. At the time of (lamination), there is a problem that air bubbles are easily entrained due to residual air. That is, recently, the number of pixels to be formed in a certain area tends to increase with the high definition of the liquid crystal display device.
Since the gap between the pixels is narrower, the bubbles are more likely to be generated when the transfer speed is increased. Since predetermined pixels are not formed in the region where the bubbles are generated,
Pixel defects (so-called white spots) and the like are generated, which causes deterioration in display accuracy and quality of the color filter. In the manufacture of the spacer, the spacer is chipped in the region where the bubble is generated, and similarly, in the alignment control structure, the chip is generated in the region where the bubble is generated.

In order to improve the productivity, it is necessary to increase the laminating speed. However, when the laminating speed is increased, air bubbles are likely to be generated. Furthermore, under the circumstance where applied devices are diversified, there is a tendency that the necessity of laminating on the surface of a substrate (substrate) other than glass or a substrate (substrate) having irregularities on the surface tends to increase, and bubbles are generated. The situation where it is easy to get involved is increasing.

[0008]

As described above, when a resin laminate such as a color filter is manufactured by the transfer method, the generation of bubbles during lamination is suppressed, and the laminating speed (higher speed) and the number of pixels formed are reduced. There has not yet been provided a manufacturing method capable of laminating a high-precision resin laminate at a high speed without depending on high definition of the resin and diversification of a substrate (substrate) to be laminated. It is the current situation.

An object of the present invention is to solve the above conventional problems and achieve the following objects. That is, the present invention suppresses the generation of bubbles during transfer by the lamination method, and provides a method of manufacturing a resin laminate capable of forming a high-precision, low-cost resin laminate without defects at high speed and in a stable manner. The purpose is to provide. Another object of the present invention is to provide a high-definition color filter which can be obtained at low cost by the method for producing a resin laminate of the present invention and has no pixel defects (white spots).

[0010]

Means for solving the above problems are as follows. That is, <1> the protective film is removed from a photosensitive resin material having a photosensitive resin layer and a protective film on a support, and the photosensitive resin layer of the photosensitive resin material is laminated on the surface of the substrate. A method of manufacturing a resin laminate including a step of transferring a photosensitive resin layer onto the substrate by peeling the support after lamination, wherein the surface free energy at the time of lamination of at least the surface of the substrate to be transferred is Wherein the polar component is 35 dyne / cm or less.

<2> The method for producing a resin laminate according to <1>, wherein a polar component of surface free energy at the time of lamination of at least the surface of the substrate to be transferred is 30 dyne / cm or less. <3> The polar component of the surface free energy at the time of lamination of at least the surface to be transferred of the substrate is 25.
The method for producing a resin laminate according to <1>, wherein the dyne / cm is not more than dyne / cm. <4> The polar component of the surface free energy at the time of lamination of at least the surface to be transferred of the substrate is 20
The method for producing a resin laminate according to <1>, wherein the dyne / cm is not more than dyne / cm. <5> The polar component of the surface free energy at the time of lamination of at least the surface to be transferred of the substrate is 15
The method for producing a resin laminate according to <1>, wherein the dyne / cm is not more than dyne / cm.

<6> The protective film is removed from a photosensitive resin material having a photosensitive resin layer and a protective film on a support, and the photosensitive resin layer of the photosensitive resin material is laminated on the surface of the substrate. Then, in a method for producing a resin laminate including a step of transferring a photosensitive resin layer onto the substrate by peeling off the support after lamination, the surface free energy at the time of lamination of at least the surface to be transferred of the substrate After adjusting the polar component to 35 dyne / cm or less, and laminating and laminating a photosensitive resin layer on the surface.

<7> The method according to any one of <1> to <6>, wherein the polar component of the surface free energy is 35 dyne / cm or less and the surface free energy dispersion component is 40 dyne / cm or less at the time of lamination. This is a method for producing a resin laminate. <8> The dispersion component of surface free energy is 30 dyne
/ Cm or less, which is the method for producing a resin laminate according to <7>. <9> Dispersion component of surface free energy is 20 dyne
/ Cm or less, which is the method for producing a resin laminate according to <7>.

<10> The resin laminate according to any one of <1> to <9>, wherein the surface free energy of the surface of the photosensitive resin layer of the photosensitive resin material at the time of lamination is 50 dyne / cm or less. It is a manufacturing method. <11> A color filter obtained by the method for producing a resin laminate according to any one of <1> to <10>.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a resin laminate of the present invention, the polar component of surface free energy is 35 dyn.
A photosensitive resin layer of a photosensitive resin material is transferred to the surface of the substrate having a thickness of e / cm or less by a lamination method. The color filter of the present invention is manufactured by the method for manufacturing a resin laminate of the present invention. Hereinafter, a method for producing a resin laminate of the present invention and a color filter obtained by the method will be described in detail.

<Production Method of Resin Laminate> The method for producing a resin laminate of the present invention uses a photosensitive resin material having a photosensitive resin layer and a protective film on a support, and protects the photosensitive resin material from the photosensitive resin material. After removing the film, the photosensitive resin layer of the photosensitive resin material is laminated on the surface of the substrate which is the object to be transferred and laminated, and the support of the photosensitive resin material after the lamination is peeled off on the substrate. The resin laminate having at least the photosensitive resin layer on the substrate is manufactured by transferring the photosensitive resin layer. Here, in the first aspect of the present invention, the polar component of the surface free energy at the time of lamination (transfer) of at least the surface to be transferred is 3
In the second embodiment of the present invention, the polar component of the surface free energy of at least the surface of the substrate to be transferred at the time of lamination (transfer) is 35 dyne / cm. cm or less, and a photosensitive resin layer is overlaid on the surface to perform lamination.

The surface free energy at the time of lamination means the surface free energy at a heating temperature when a photosensitive resin material is superposed on a substrate surface, and a photosensitive resin layer is laminated and transferred onto the substrate surface. The surface free energy is determined by measurement according to a measurement example described later.
By setting the surface free energy of the surface to be transferred within the above range, the photosensitive resin layer 2 melted by heating during laminating is uniformly laminated on the surface of the substrate 1 as shown in FIG. I can go. That is, FIG.
As shown in (B), when the surface energy of the transfer surface of the substrate is large, the affinity between the photosensitive resin layer 2 and the surface of the substrate 1 is improved, and the wettability is increased. It is presumed that as a result, the photosensitive resin layer 2 that has been melted goes around the substrate side, so that air is easily taken into the resin.

Here, as described above, the surface of the photosensitive resin material to which the photosensitive resin layer is transferred (hereinafter referred to as the “transfer surface”).
There is that. ), The polar component of the surface free energy at the time of lamination (transfer) is 35 dyne / cm
The polar component is preferably as small as possible in view of the effect of avoiding the incorporation of bubbles, particularly preferably 30 dyne / cm or less, more preferably 25 dyne / cm or less,
Particularly preferred is 20 dyne / cm or less, and 15 dyne / cm or less.
/ Cm or less is most preferred.

In order to more effectively prevent the mixing of bubbles during lamination, the polar component of the surface free energy during lamination (transfer) is set to 35 dyne / cm or less, and the dispersion component of the surface free energy is reduced. 40
It is preferable to be dyne / cm or less. The dispersing component is also preferably smaller in view of the effect of avoiding the incorporation of bubbles, particularly preferably 30 dyne / cm or less, particularly preferably 20 dyne / cm or less. here,
As the surface free energy at the time of lamination (transfer), the value of the polar component and the value of the dispersive component may be arbitrarily combined as appropriate from the range of the polar component and the dispersive component (including the preferable range). it can. For example,
The polar component may be in a range of 35 or less and the dispersed component may be in a range of 20 or less, the polar component may be in a range of 30 or less and the dispersed component may be in a range of 30 or less, and the polar component may be in a range of 30 or less. The dispersion component may be in the range of 40 or less.

The characteristics of the photosensitive resin layer melted during lamination to the substrate surface with respect to the incorporation of bubbles are easily affected by the balance between the polar component and the dispersed component of the surface free energy on the surface to be transferred. By doing so, the generation of air bubbles (bubbles) can be effectively prevented.

In the method for producing a resin laminate of the present invention, the polar component of the surface free energy of the surface to be transferred onto which the photosensitive resin layer of the photosensitive resin material is to be transferred is used as the member to be transferred. At 35 dyne / cm
The following substrate (first embodiment) or the surface free energy of the transfer surface has a polar component of 35 dyne / c.
m, the surface to be transferred is subjected to treatment, and the polar component of surface free energy during lamination (transfer) is controlled (adjusted) to 35 dyne / cm or less.
Using a substrate having a treated surface (second embodiment), the polarity component of the substrate at the time of lamination (transfer) is 35%.
Laminating is performed by superposing a photosensitive resin layer on the surface of dyne / cm or less. In the second embodiment, the method includes a step of lowering (controlling) the surface free energy of the transfer surface of the substrate to the above range, using the following method,
This step may be provided at any stage before lamination.

As a method of lowering (controlling) the surface free energy of the transfer surface of the substrate to the above range, for example, physical vapor deposition (PVD: vacuum deposition, ion plating, sputtering), chemical Deposition (C
VD), a plasma treatment method using glow discharge, corona discharge, high frequency discharge, microwave discharge, a coating method using a surface treatment agent such as a surfactant, a silane coupling agent, a titanate coupling agent, and the like. Many surface treatment methods are applicable. Further, a heat treatment or the like may be performed after the coating of the surface treatment agent. Furthermore, after performing these surface treatments, it may be aged until the surface free energy changes to a desired range. However, the present invention is not limited to these.

Examples of the sputtering method include bipolar sputtering, tripolar sputtering, quadrupolar sputtering, magnetron sputtering, high frequency sputtering, reactive sputtering, bias sputtering, asymmetric sputtering, getter sputtering and the like.

The surface treating agent suitable for the purpose of the present invention includes, as the surfactant, for example, carboxylate,
Anionic surfactants such as sulfonates, sulfates, phosphates, and formalin condensation sulfonates; aliphatic amine salts and their quaternary ammonium salts, aromatic quaternary ammonium salts, pyridinium salts, imidazoli Cationic surfactants such as ammonium salts; amphoteric surfactants such as betaines, aminocarboxylates and imidazoline derivatives; nonionic surfactants such as ethers, ether esters and ester nitrogen-containing aliphatic alkanolamides;
Fluorinated surfactants; polypeptide derivatives, natural surfactants and the like.

Further, as the coupling agent, for example, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2
-(Aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane,
N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-
Examples thereof include silane coupling agents such as chloropropyltrimethoxysilane, and titanium-based coupling agents.

In addition to the above, as a method of controlling the surface free energy of the surface to be transferred, an organic pigment, various waxes, metal soap, a binder,
A method in which a solvent, a lubricant, or the like, or all or some of the components contained in the photosensitive resin layer described below are coated before lamination may be used, and the same effect can be obtained.

Specifically, the organic pigment includes, for example, zinc oxide, calcium carbonate, barium sulfate, titanium oxide, lithopone, talc, limestone, kaolin, aluminum hydroxide, amorphous silica, styrene resin, formalin condensation , A fluoroethylene resin, a urea resin, and the like. Examples of the metal soap include emulsions of higher fatty acid metal salts such as calcium stearate and aluminum stearate, and the wax includes, for example, stearic acid. , Paraffin wax, microcrystalline wax, carnauba wax, methylol stearamide, polyethylene wax, silicone, and emulsions thereof.

Examples of the binder include polyolefins such as polyethylene, polypropylene, and polystyrene; vinyl resins such as polyvinyl chloride, polyvinyl alcohol, and carboxy-organized polyvinyl alcohol; phenol resins; and fluororesins (for example, fluorine coating agents); Polyamide, polyimide, polyacetal, (meth) acrylic resin, polycarbonate, saturated or unsaturated polyester, urethane resin, alkyd resin,
Various resins such as epoxy resin and silicone resin; various fibers such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose; various proteins such as starches and gelatin.

The solvent is preferably a water-miscible solvent, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol. Mono-n-butyl ether, benzyl alcohol,
Acetone, methyl ethyl ketone, cyclohexanone, ε
-Caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the solvent miscible with water is generally 0.1 to 30% by mass.

Examples of all or a part of the components contained in the photosensitive resin layer include a photosensitive resin composition.
All those described in JP-A-282404 can be used. Examples thereof include a photosensitive resin composition comprising a negative-type diazo resin and a binder, a photopolymer composition, a photosensitive resin composition comprising an azide compound and a binder, and a cinnamic acid-type photosensitive resin composition. ,In particular,
A layer made of a photosensitive resin composition containing an alkali-soluble binder polymer, a monomer having an ethylenically unsaturated double bond that undergoes addition polymerization upon irradiation with light, a photopolymerization initiator, and a colorant is preferable. Further, other components such as a thermal polymerization inhibitor may be contained.

Examples of the alkali-soluble binder polymer include a polymer having a carboxylic acid group in a side chain, a cellulose derivative having a carboxylic acid group in a side chain, and a polymer having a hydroxyl group and a cyclic acid anhydride added thereto. Can be Examples of the polymer having a carboxylic acid group in the side chain include, for example, JP-A-59-44615,
JP-B-54-34327, JP-B-58-1257
No. 7, JP-B-54-25957, JP-A-59
-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid Acid copolymers and the like can be mentioned. Examples of the polymer having a hydroxyl group to which a cyclic acid anhydride is added include, in particular, US Pat. No. 4,139,391.
And benzyl (meth) acrylate and (meth) acrylic acid, and a multi-component copolymer of benzyl (meth) acrylate and (meth) acrylic acid with other monomers. .

Among the alkali-soluble binder polymers, an acid value in the range of 50 to 300 mg KOH / g and 1
It is preferable to select and use those having a mass average molecular weight in the range of 000 to 300,000.

For the purpose of improving various properties such as the strength of the cured film, for example, an alkali-insoluble polymer can be added as long as it does not adversely affect the developability and the like. As the polymer, alcohol-soluble nylon,
Epoxy resins and the like can be mentioned. The content of the alkali-soluble binder polymer is preferably from 10 to 95% by mass of the total solid content (mass) of the photosensitive resin layer, and is preferably from 20 to 9%.
0 mass% is more preferable. When the content is less than 10% by mass, the adhesiveness of the photosensitive resin layer may be too high. When the content is more than 95% by mass, the photosensitivity and the color layer (colored image) or black matrix to be formed may be formed. May be inferior in strength.

The monomer having an ethylenically unsaturated double bond which undergoes addition polymerization upon irradiation with light has at least one addition-polymerizable ethylenically unsaturated group in the molecule and has a boiling point of 100 at normal pressure. These compounds are mentioned.
For example, monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) )ether,
Tri (acryloyloxyethyl) isocyanurate,
Tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding propylene oxide to ethylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated And so on.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193;
No. 4183, JP-B-49-43191 and JP-B-52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. And the like.

Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferred.

The polymerizable monomers may be used alone or as a mixture of two or more. The content of the monomer having an ethylenically unsaturated double bond that undergoes addition polymerization upon irradiation with the light is generally 5 to 50% by mass of the total solid content (mass) of the photosensitive resin layer, and is particularly preferably 10 to 50% by mass. 40% by mass is preferred. The content is 5% by mass.
If it is less than 50%, the photosensitivity and the strength of the colored layer (colored image) or the black matrix may be reduced, and the content may be reduced to 50% by mass.
If the ratio exceeds the above range, the adhesiveness of the photosensitive resin layer becomes excessive, which is not preferable.

Examples of the photopolymerization initiator include a vicinal polyketaldonyl compound described in US Pat. No. 2,367,660, an acyloin ether compound described in US Pat. No. 2,448,828, and US Pat.
No. 2512, an aromatic acyloin compound substituted with an α-hydrocarbon, a polynuclear quinone compound described in U.S. Pat. Nos. 3,046,127 and 2,951,758, and U.S. Pat. No. 3,549,367. Combinations of the described triarylimidazole dimer and p-aminoketone, the benzothiazole compounds and trihalomethyl-s-triazine compounds described in JP-B-51-48516, and the trihalides described in U.S. Pat. No. 4,239,850. Examples include a methyl-s-triazine compound and a trihalomethyloxadiazole compound described in U.S. Pat. No. 4,221,976. Among them, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimer are particularly preferred.

The content of the photopolymerization initiator is generally 0.5 to 20% by mass of the total solid content (mass) of the photosensitive resin layer, and preferably 1 to 15% by mass. The content is
If the amount is less than 0.5% by mass, the photosensitivity and the strength of the colored layer (colored image) or the black matrix may be reduced, and even if it exceeds 20% by mass, the performance is further improved. No effect is observed.

As the colorant, red, green, blue and black pigments which are constituent colors of a color filter are generally used. For example, Carmine 6B (CI.1249)
0), phthalocyanine green (CI. 7426)
0), phthalocyanine blue (C.I. 74160),
Preferable examples include carbon black. As the content of the colorant, the total solid content (mass) of the photosensitive resin layer
Is preferably 1 to 30% by mass, and particularly preferably 5 to 20% by mass.

It is preferable that the composition further contains a thermal polymerization inhibitor in addition to the above components. As the thermal polymerization inhibitor, for example,
Hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-
Mercaptobenzimidazole, phenothiazine and the like. Further, known additives such as a plasticizer, a surfactant, a solvent and the like can be added.

Further, the surface roughness may be controlled by polishing or lapping the transferred surface of the substrate, or the surface may be mechanochemically modified by friction with the polishing material. For example, abrasives for polishing the surface of glass include, for example, aluminum oxide, chromium oxide, iron oxide, diamond powder, and the like.

The above surface treatment method may be performed alone or in combination of a plurality of types according to the type of the substrate.
In addition, when a laminate is repeated a plurality of times on the same substrate, such as a color filter, the surface treatment is not necessarily a drink before the first pattern formation.
It can also be applied before the formation of the third pattern. That is, in the present invention, it is important that the surface free energy at the time of lamination be in the above range.

As a method of measuring the surface free energy,
There is no particular limitation, and the following method is given as an example.
Surface free energy γ_SIs the dispersion component γ of the surface tension_S ^dWhen
Polar component γ of surface tension_S ^pAnd γ_S= Γ_S ^d+ Γ_S ^pIn table
Is done. That is, the surface free energy was assumed to be a liquid
Sometimes it is expressed by the surface tension that tries to contract by itself
is there.

Here, the surface free energy of a certain two liquids is γ ₁ and γ ₂ , and the polar components of the surface tension are γ ₁ ^d and γ ₂ ^d ,
Assuming that the polar components of the surface tension are γ ₁ ^p and γ ₂ ^p and the contact angles of the two liquids on the surface for which the surface free energy is to be determined are θ ₁ and θ ₂ , the following equation is established.

[0046]

(Equation 1)

Therefore, the two liquids whose surface free energies (polar component and dispersion component) are known are placed on the surface (surface to be measured) whose surface free energy is to be measured, and the respective contact angles θ ₁ and θ ₂ are measured. For example, using the above equation, the dispersion component γ _S ^d of the surface tension of the surface to be measured and the polarity component γ _S ^p of the surface tension are measured.
Can be obtained, and the surface free energy γ _S of the surface to be measured can be obtained from the sum. For example,
The surface free energy of water has a dispersion component (γ _d ) of surface tension of 21.8 dyne / cm and a polar component (γ _p ) of surface tension of 51.0 dyne / cm, and the surface free energy of methylene iodide is The dispersion component (γ _d ) of the surface tension is 48.5 dyne / cm, and the polarity component (γ _p ) of the surface tension is 2.3 dyne / cm.
The surface free energy may be determined using a liquid.

The surface free energy may change with the temperature rise on the surface. For example, when the surface free energy at room temperature (25 ° C.) is measured,
The measured value is the surface free energy (polar component and / or
Or a dispersion component), it is possible to avoid air bubbles during lamination (for example, at a substrate surface temperature of 80 ° C (heating temperature of 130 ° C or the like)). Since the surface free energy of glass is slightly increased by heating, it is necessary that the surface free energy at the moment of lamination falls within the above range.

As described above, the surface free energy of the surface to be transferred (the substrate surface on the side to be transferred) at the time of lamination (transfer) is changed with respect to the substrate surface of the photosensitive resin layer which is heated and melted during lamination. By controlling the wettability to be improved, it is possible to effectively avoid the incorporation of air bubbles (bubbles) which are likely to occur during the close transfer.
That is, for example, even when the laminating speed is increased for the purpose of cost reduction, or when the image is transferred to an already uneven surface, mixing of bubbles (bubbles) is suppressed, and It is possible to stably form a high-precision resin laminate at low cost without defects that may cause transfer failure.

In the present invention, the basic manufacturing method is as follows. The method for producing a resin laminate according to the present invention,
Basically, after removing the protective film from the photosensitive resin material described later, the photosensitive resin layer of the photosensitive resin material is overlaid on the surface of the substrate and laminated, and the support of the laminated photosensitive resin material is laminated. A step of transferring the photosensitive resin layer onto a substrate by peeling (hereinafter, also referred to as a “transfer step”), and preheating the photosensitive resin material at the time of transfer, if necessary. The preheating step may include other steps such as a heat treatment step for curing, and finally, the laminated body having at least the photosensitive resin layer on the transferred substrate, A patterned resin laminate (for example, a color filter, a spacer, etc.) can be manufactured through an exposure step, a development step, and the like.

[Transfer Step] In the transfer step, the surface of the photosensitive resin layer of the photosensitive resin material from which the protective film has been peeled off is disposed so as to face the surface of the substrate to be transferred, and the surface of the substrate is exposed to light. The laminate is brought into contact with the conductive resin layer and laminated, and the laminated state is pasted through a lamination roller under pressure and heat (lamination). Before the lamination, a step of preheating the photosensitive resin material may be provided as a pretreatment. After bonding, the support is peeled from the obtained laminate.

For the lamination, a conventionally known laminating apparatus or vacuum laminating apparatus can be used. In order to further increase the productivity, an automatic cut laminator device is also suitable. As the heating temperature at the time of bonding, it is necessary to sufficiently soften the photosensitive resin layer, and the temperature of the substrate surface is preferably 25 to 150 ° C., more preferably 50 to 140 ° C., and the lamination is performed in this temperature range. It is preferable that the surface free energy (polar component and / or dispersion component) of the substrate surface (transferred surface) at this time be in the range described above. By setting the surface free energy (polar component and / or dispersion component) of the substrate in the range of the temperature of the laminating roll, that is, the surface temperature of the substrate surface as described above, the molten photosensitive resin layer Laminate and transfer can be performed at high speed and uniformly without involving air bubbles (bubbles) on the surface.

[Exposure Step] In the exposure step, the photosensitive resin layer on the substrate is irradiated with light through a predetermined photomask and, if necessary, a thermoplastic resin layer and an oxygen barrier layer. When the photosensitive resin layer is irradiated with light in a pattern, the exposed portions of the photosensitive resin layer are cured.

The light source that can be used for the light irradiation is appropriately selected according to the photosensitivity of the photosensitive resin layer. For example, a known light source such as an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, and an argon laser is used. Is mentioned. JP-A-6-591
As described in JP-A No. 19, an optical filter having a light transmittance of 2% or less at a wavelength of 400 nm or more may be used in combination.

When a plurality of colored layers are formed by transfer in the production of a color filter, air remains in the gap between adjacent pixels when laminating (transferring) photosensitive resin materials of the second color and thereafter. In order to prevent this, a photomask in which a rectangular opening in a pixel pattern portion is chamfered may be used. The position and shape of the chamfer are described in Japanese Patent Application No. 9-044644.

When the photosensitive resin material has a thermoplastic resin layer, the thermoplastic resin layer may be peeled off together with the support, or may be peeled off when the support is peeled off. Separately, it may be peeled off after exposure.

[Developing Step] In the developing step, the exposed photosensitive resin layer on the substrate is developed using a developing solution. By the treatment, the non-exposed portion (uncured portion) of the photosensitive resin layer, and when the photosensitive resin material has a thermoplastic resin layer and an oxygen barrier layer, the thermoplastic resin layer and the oxygen barrier layer The removed resin laminate (in the case of a color filter, a large number of minute colored layers (colored pixels)) can be formed.

As the developing solution, a dilute aqueous solution of an alkaline substance is preferable, and a developing solution to which a small amount of an organic solvent miscible with water may be added may be used. Examples of the alkaline substance include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (eg, sodium carbonate, potassium carbonate, etc.),
Alkali metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate, etc.), alkali metal silicates (eg, sodium silicate, potassium silicate, etc.), alkali metal metasilicates (eg, sodium metasilicate, metasilicate) Potassium), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg, tetramethylammonium hydroxide, etc.), and trisodium phosphate. The concentration of the alkaline substance is preferably from 0.01 to 30% by mass, and the pH is preferably from 8 to 14.

In the case of a photosensitive resin layer of RGB or the like, excluding a light-shielding photosensitive black resin layer to be described later, for example, by using a developer having a relatively low pH, development by film detachment is preferable. Can be done.

As the organic solvent miscible with water, for example,
Methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent miscible with water is generally 0.1 to 30% by mass. Further, a known surfactant may be further added to the developer, and the concentration of the surfactant may be 0.01 to 10%.
% By mass is preferred.

The developer may be used as a bath liquid or a spray liquid. In order to remove the uncured portion of the photosensitive resin layer in a solid form (preferably in a film form), a method such as rubbing with a rotating brush or a wet sponge in a developer or spraying the developer is used. The method using the spray pressure of the above is preferable. The temperature of the developer is usually preferably in the range of around room temperature to 40 ° C. A water washing step may be added after the development processing.

[Other Steps] After the development step, the formed patterned resin laminate (colored layer (colored pixel) in the case of a color filter) is sufficiently cured to improve chemical resistance. Further, a heat treatment is preferably performed. As the heat treatment, a substrate having a patterned resin laminate is heated in an electric furnace, a drier, or the like, or heated by irradiating an infrared lamp to the patterned resin laminate,
And the like. Heating temperature in this case,
The time depends on the composition of the photosensitive resin layer and the thickness of the resin laminate, but in general, in order to secure sufficient solvent resistance and alkali resistance, a temperature of about 120 to 250 ° C.
About 10 to 300 minutes are preferred.

As described above, a substrate having a resin laminate (in the case of a color filter, a colored layer (colored pixel pattern) of one color) is obtained. In the color filter, a multicolor color filter is obtained by repeating the above-described steps by a necessary number of colors using a photosensitive resin material having a photosensitive resin layer of another hue on the substrate. be able to.

The color filter may be composed of only one color (all the same color), or may be composed of two or more colors. Also, for example, red,
When arranging three color pixels of green and blue, stripe type,
Any arrangement of a mosaic type, a triangle type, a four-pixel arrangement type, or the like may be used. Further, using a photosensitive resin material for forming a black layer (a photosensitive resin material for forming a black matrix) having a black photosensitive resin layer (a photosensitive black resin layer), in the same manner as described above, RGB or the like is already used. The photosensitive black resin layer of the photosensitive resin material for forming a black matrix is transferred to the surface of the substrate on which the colored layer (colored pixel) is formed on the side having the colored pixel. A black resin layer, that is, a black matrix (light-shielding image) can be formed so as to fill gaps between pixels by performing exposure (backside exposure), development, and heat treatment from the surface on the non-use side. Thereby, a color filter with a black matrix is obtained.

The back exposure can be generally performed by irradiation of ultraviolet rays (UV), but the type of light is appropriately selected according to the photosensitivity of the photosensitive black resin layer. In addition, the thickness of the black matrix to be formed is preferably 0.5 to 3 μm. In order that the black matrix is not formed in the shape of a protrusion and the surface of the formed color filter exhibits good flatness, the transfer is performed. The photosensitive black resin layer (black matrix) is preferably the same thickness as or less than the thickness of the colored layer (colored pixel).

As another step, a step of preheating the photosensitive resin material before transfer may be provided. By heating in advance, irregularities on the surface of the photosensitive resin layer can be eliminated, and the image can be transferred while the surface of the photosensitive resin layer is flat, so that bubbles (bubbles) that are likely to be generated at the time of high-speed lamination Can be more effectively suppressed. In addition, when a photosensitive resin material that has undergone a temporal change is used, air bubbles can be prevented from being mixed, and lamination can be performed more stably at high speed. However, the preheating is preferably performed after the removal of the protective film, from the viewpoint that the protective film shrinks and causes wrinkles of the photosensitive resin material and does not increase surface irregularities. The heating temperature at the time of preheating the photosensitive resin material is preferably 40 to 150 ° C, and 50 to 120 ° C.
Is more preferred.

<Photosensitive resin material> Next, the photosensitive resin material used in the method for producing a resin laminate of the present invention will be described in detail. The photosensitive resin material is preferably a film-shaped photosensitive resin material, but is not limited thereto.For example, a long photosensitive resin colored sheet that can be used for manufacturing a color filter, And a photosensitive black sheet for forming a black matrix.

The photosensitive resin material has at least a photosensitive resin layer and a protective film in this order on a support. If necessary, other layers such as a thermoplastic resin layer and an oxygen barrier layer may be used. You may have.

(Support) The support is made of a material which is flexible, has good peelability with respect to a photosensitive resin layer or a thermoplastic resin layer, and is chemically and thermally stable. Is preferred. Specifically, a film of Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene or the like or a laminate thereof is preferable. To have good releasability from the photosensitive resin layer or thermoplastic resin layer, etc., without surface treatment such as glow discharge,
In general, no undercoat layer such as gelatin is provided. The thickness of the support is suitably from 5 to 300 μm, particularly preferably from 20 to 150 μm.

(Photosensitive Resin Layer) The photosensitive resin layer is a layer containing a photosensitive resin composition and a coloring agent.
It shows softening or tackiness at a temperature of 0 ° C. or higher, and is preferably thermoplastic. Most layers of known photopolymerizable compositions have this property. The layer can be further modified by adding a thermoplastic resin or a compatible plasticizer. The layer thickness of the photosensitive resin layer is 0.5 to
3 μm is preferred, usually about 2 μm.

Further, from the viewpoint of improving the wettability of the photosensitive resin layer on the surface of the substrate and more effectively preventing the generation of bubbles when laminating and transferring, the surface of the photosensitive resin layer is The surface free energy at the time of lamination (transfer) is preferably set to 50 dyne / cm or less. As a result, the surface free energy close to the surface of the substrate described above can be obtained. For example, as shown in FIG.
Can be more uniformly laminated. The surface free energy is measured and obtained by the above-described measurement example. Here, the surface free energy at the time of lamination (transfer) means the heating temperature at the time of lamination, that is, the surface free energy when the surface temperature of the substrate surface to be transferred is 40 to 150 ° C.

As a method of lowering (controlling) the surface free energy of the surface of the photosensitive resin layer which comes into contact with the substrate, the surface of the photosensitive resin layer is heated in a normal atmosphere such as air at normal temperature. To introduce a CO group on the surface.

As the photosensitive resin composition, for example,
All those described in JP-A-3-282404 can be used. Examples thereof include a photosensitive resin composition comprising a negative-type diazo resin and a binder, a photopolymer composition, a photosensitive resin composition comprising an azide compound and a binder, and a cinnamic acid-type photosensitive resin composition. ,
Specifically, a layer composed of a photosensitive resin composition containing an alkali-soluble binder polymer, a monomer having an ethylenically unsaturated double bond that undergoes addition polymerization upon irradiation with light, a photopolymerization initiator, and a colorant is suitable. Further, other components such as a thermal polymerization inhibitor may be contained.

Examples of the alkali-soluble binder polymer include a polymer having a carboxylic acid group in a side chain, a cellulose derivative having a carboxylic acid group in a side chain, and a polymer having a hydroxyl group added with a cyclic acid anhydride. Can be

Examples of the polymer having a carboxylic acid group in the side chain include, for example, JP-A-59-44615, JP-B-54-34327, and JP-B-58-12577.
JP, JP-B-54-25957 and JP-A-59-5957.
No. 53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid And copolymers.

Examples of the above-mentioned polymer having a hydroxyl group to which a cyclic acid anhydride is added include, in particular, US Pat.
No. 391, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid or benzyl (meth)
A multicomponent copolymer of acrylate, (meth) acrylic acid and another monomer can be exemplified.

Among the alkali-soluble binder polymers, an acid value in the range of 50 to 300 mg KOH / g and 1
It is preferable to select and use those having a mass average molecular weight in the range of 000 to 300,000.

For the purpose of improving various properties such as the strength of the cured film, for example, an alkali-insoluble polymer can be added as long as it does not adversely affect the developability and the like. As the polymer, alcohol-soluble nylon,
Epoxy resins and the like can be mentioned.

The content of the alkali-soluble binder polymer is 1% of the total solid content (mass) of the photosensitive resin layer.
0-95 mass% is preferred, and 20-90 mass% is more preferred. When the content is less than 10% by mass, the tackiness of the photosensitive resin layer may be too high, and when the content is more than 95% by mass, the photosensitivity and the colored layer (colored image) to be formed.
And the strength of the black matrix may be inferior.

The monomer having an ethylenically unsaturated double bond which is addition-polymerized by irradiation with light (hereinafter, may be referred to as “polymerizable monomer”) includes at least one polymerizable ethylene in the molecule. Compounds having an unsaturated group and having a boiling point of 100 or more at normal pressure. For example, monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate,
Neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate , Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; Examples include polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding an oxide and then (meth) acrylated.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193;
No. 4183, JP-B-49-43191 and JP-B-52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. And the like.

Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferred.

The polymerizable monomers may be used alone or as a mixture of two or more. The content of the monomer having an ethylenically unsaturated double bond that undergoes addition polymerization upon irradiation with the light is generally 5 to 50% by mass of the total solid content (mass) of the photosensitive resin layer, and is particularly preferably 10 to 50% by mass. 40% by mass is preferred. The content is 5% by mass.
If it is less than 50%, the photosensitivity and the strength of the colored layer (colored image) or the black matrix may be reduced, and the content may be reduced to 50% by mass.
If the ratio exceeds the above range, the adhesiveness of the photosensitive resin layer becomes excessive, which is not preferable.

Examples of the photopolymerization initiator include a vicinal polyketaldonyl compound described in US Pat. No. 2,367,660, an acyloin ether compound described in US Pat. No. 2,448,828, and US Pat.
No. 2512, an aromatic acyloin compound substituted with an α-hydrocarbon, a polynuclear quinone compound described in U.S. Pat. Nos. 3,046,127 and 2,951,758, and U.S. Pat. No. 3,549,367. Combinations of the described triarylimidazole dimer and p-aminoketone, the benzothiazole compounds and trihalomethyl-s-triazine compounds described in JP-B-51-48516, and the trihalides described in U.S. Pat. No. 4,239,850. Examples include a methyl-s-triazine compound and a trihalomethyloxadiazole compound described in U.S. Pat. No. 4,221,976. Among them, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimer are particularly preferred.

The content of the photopolymerization initiator is generally from 0.5 to 20% by mass of the total solid content (mass) of the photosensitive resin layer, preferably from 1 to 15% by mass. The content is
If the amount is less than 0.5% by mass, the photosensitivity and the strength of the colored layer (colored image) or the black matrix may be reduced, and even if it exceeds 20% by mass, the performance is further improved. No effect is observed.

As the colorant, red, green, blue and black pigments which are constituent colors of a color filter are generally used. For example, carmine 6B (CI.1249)
0), phthalocyanine green (CI. 7426)
0), phthalocyanine blue (C.I. 74160),
Preferable examples include carbon black. As the content of the colorant, the total solid content (mass) of the photosensitive resin layer
Is preferably 1 to 30% by mass, and particularly preferably 5 to 20% by mass.

It is preferable that the composition further contains a thermal polymerization inhibitor in addition to the above components. As the thermal polymerization inhibitor, for example,
Hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-
Mercaptobenzimidazole, phenothiazine and the like. Further, known additives such as a plasticizer, a surfactant, a solvent and the like can be added.

(Protective Film) The protective film is preferably a material which is flexible like the above-mentioned support, has good releasability from the photosensitive resin layer, and is chemically and thermally stable. . Specifically, a film of polypropylene, Teflon, polyethylene terephthalate, polycarbonate, polyethylene or the like or a laminate thereof is preferable. The thickness of the protective film is suitably from 0.1 to 20 μm, and particularly preferably from 5 to 15 μm.

(Others) The above-mentioned photosensitive resin material may be provided with a thermoplastic resin layer and an oxygen blocking layer, if necessary. -Thermoplastic resin layer- When the thermoplastic resin layer is transferred onto a substrate that is an object to be transferred, it exhibits a function as a cushion material for preventing a transfer failure that may occur due to unevenness existing on the substrate, It is provided for the purpose of preventing air bubbles from entering during lamination (transfer),
Contains alkali-soluble thermoplastic resin as the main component,
Other components may be included.

The resin constituting the thermoplastic resin layer is preferably a resin which is thermoplastic and has a property of being deformed in accordance with the irregularities when heated and adhered, and is soluble in an alkaline aqueous solution after transfer, that is, an alkaline aqueous solution. It is.

The alkali-soluble thermoplastic resin is alkali-soluble and has a substantial softening point of 80 ° C.
The following thermoplastic resins are mentioned, for example, saponified products of ethylene and acrylate copolymer, saponified products of styrene and (meth) acrylate copolymer, vinyl toluene and (meth) acrylate copolymer And poly (meth) acrylates, and saponified products such as (meth) acrylate copolymers such as butyl (meth) acrylate and vinyl acetate.

Further, organic materials having a softening point of about 80 ° C. or lower described in “Plastic Performance Handbook” (edited by Japan Federation of Plastics Industries, All Japan Plastics Molding Industry Association, published by the Industrial Research Institute, issued on October 25, 1968). Among the polymers, those soluble in an aqueous alkali solution may also be mentioned. The thermoplastic resins may be used alone or in combination of two or more.

Further, even if the organic polymer substance has a softening point of 80 ° C. or higher, various plasticizers compatible with the polymer substance are added to the organic polymer substance to increase the substantial softening point to 80 ° C. ° C
It is also possible to use below. In the organic polymer substance, various polymers, a supercooled substance, an adhesion improver, a surfactant, and the like, for the purpose of controlling the adhesive force with the support, are further provided that the substantial softening point does not exceed 80 ° C. It is also possible to add a release agent or the like.

The plasticizer preferably includes, for example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, and the like.

The thickness of the thermoplastic resin layer is 6 μm.
m or more is preferable. If the thickness is less than 5 μm, it may be difficult to completely absorb irregularities of 1 μm or more existing on the substrate. The upper limit is generally about 100 μm or less in view of developability and manufacturing suitability, and is about 50 μm or less.
μm or less is preferred.

-Oxygen Blocking Layer- The oxygen blocking layer prevents diffusion of oxygen from the air which inhibits a photocuring reaction in the photosensitive resin layer during imagewise pattern exposure (oxygen blocking during exposure). Purpose and, for example, RG
When three layers corresponding to B are laminated, the layer is provided for the purpose of preventing mixing between the alkali-soluble thermoplastic resin layer and the photosensitive thermosetting resin layer. The oxygen barrier layer may be any material as long as it is dispersed or dissolved in water or an aqueous alkali solution and has low oxygen permeability, and a known material may be used.

For example, polyvinyl ether / maleic anhydride polymers, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, carboxyalkyl, described in JP-A-46-2121 and JP-B-56-40824. A group consisting of starch salts, water salts, polyvinyl alcohol, polyvinyl pyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches and the like. And a styrene / maleic acid copolymer, a maleate resin, and the like.
Further, a combination of two or more of these may be used.

Among them, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferred. The polyvinyl alcohol preferably has a saponification rate of 80 mol% or more. The content of the polyvinylpyrrolidone is generally 1 to 75% by mass of the solid content (mass) of the oxygen barrier layer, preferably 1 to 60% by mass,
50 mass% is more preferable. If the content is less than 1% by mass, sufficient adhesiveness to the photosensitive thermosetting resin layer may not be obtained, and if it exceeds 75% by mass, the oxygen barrier ability may be reduced. .

The thickness of the oxygen barrier layer is very thin, preferably about 0.1 to 5 μm, more preferably 0.5 to 2 μm.
m is more preferred. If the layer thickness is less than about 0.1 μm, oxygen permeability may be too high, and if it exceeds about 5 μm, it may take a long time during development or when removing the oxygen barrier layer.

The photosensitive resin material according to the present invention is prepared by applying a solution or dispersion containing the above-described photosensitive resin composition and a colorant (coating solution for a photosensitive resin layer) onto a support. After drying and drying, a protective film can be further formed by lamination or the like. When a thermoplastic resin layer or an oxygen barrier layer is provided between the support and the photosensitive resin layer, first, a coating liquid for forming a thermoplastic resin layer (a coating liquid for a thermoplastic resin layer) is applied on the support. Drying to form a thermoplastic resin layer, and then applying a coating liquid for forming an oxygen barrier layer (a coating liquid for an oxygen barrier layer) prepared using a solvent that does not dissolve the thermoplastic resin layer to the thermoplastic resin layer Coating on top and drying to form an oxygen barrier layer. Subsequently, a coating solution for a photosensitive resin layer prepared with a solvent that does not dissolve the oxygen barrier layer is applied,
Dry to form a photosensitive resin layer. Further, it can be produced by providing a protective film on the surface of the photosensitive resin layer.

<Substrate> The substrate used in the method for producing a resin laminate of the present invention is preferably a transparent substrate, for example, a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate A well-known glass plate or a plastic film is preferably used.

<Color Filter> The color filter of the present invention is obtained by the laminating method according to the above-described method for producing a resin laminate of the present invention, and a single-color or plural-color film (color pixels) and a necessary color film are formed on a substrate. And a black matrix according to That is, the color filter of the present invention is:
It has high-definition colored pixels without pixel defects and is manufactured at low cost.

[0103]

Embodiments of the present invention will be described below in detail, but the present invention is not limited to these embodiments. In the following, “parts” means “parts by mass” unless otherwise specified.
Represents (Example 1)-Preparation of substrate-The surface of an H-coated glass substrate (manufactured by Nippon Sheet Glass Co., Ltd.)
A fluorine coating agent (FP-91, manufactured by Sumitomo Chemical Co., Ltd.) was applied to obtain a substrate having a surface free energy polar component of 1 dyne / cm (surface temperature 60 ° C.) on the coated surface.

—Preparation of Photosensitive Resin Material— A coating solution having the following composition A was applied on a 75 μm-thick polyethylene terephthalate film support and dried to form a thermoplastic resin layer having a dry layer thickness of 20 μm. Provided.

[Composition A of Coating Solution for Thermoplastic Resin Layer] Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer: 4.5 parts (copolymerization ratio (molar ratio) = 55/11. 7 / 4.5 / 28.8, mass average molecular weight = 80000) Styrene / acrylic acid copolymer: 10.5 parts (copolymer composition ratio (molar ratio) = 7/3, mass average molecular weight = 8000) BPE-500: 7.0 parts (polyfunctional acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) F177P: 0.26 parts (fluorinated surfactant, manufactured by Dainippon Ink Co., Ltd.) Methanol: 30.6 parts・ Methyl ethyl ketone: 18.6 parts ・ 1-Methoxy-2-propanol: 9.3 parts

Next, a coating solution having the following composition B was applied on the thermoplastic resin layer and dried to form an oxygen barrier layer having a dry layer thickness of 1.6 μm. [Composition B of oxygen blocking layer coating solution] Polyvinyl alcohol (PVA205, 80% saponification degree, manufactured by Kuraray Co., Ltd.) 13 parts Polyvinylpyrrolidone 6 parts (PVP, K-30 manufactured by GAF Corporation) Methanol: 173 parts ・ Distilled water: 211.4 parts

As described above, two supports provided with a thermoplastic resin layer and an oxygen barrier layer are prepared, and red (R) and green having the compositions shown in Table 1 below are provided on each of the oxygen barrier layers. The coating solution (coating solution for the photosensitive resin layer) for forming each layer (R layer, G layer) of (G) is applied and dried, and the dried layer thickness becomes 2
A photosensitive resin layer having a thickness of μm was formed. Further, a protective film of polypropylene (thickness: 12 μm) is formed on the photosensitive resin layer.
m) was pressed to produce two types of photosensitive resin materials for forming red (R) and green (G) pixels.

[0108]

[Table 1]

-Manufacture of Color Filter- With respect to the two kinds of photosensitive resin materials obtained as described above, a color filter was manufactured using a laminating apparatus after a lapse of the second half of the manufacture.

[Transfer Step] First, the protective film was peeled off from the photosensitive resin material for forming the red (R) pixel, and the surface of the substrate obtained above was coated with the photosensitive resin material. The surfaces of the resin layers are overlapped, and using a laminator (Auto Cut Laminator ASL-24, manufactured by Somar Corporation), the wrap angle between the photosensitive resin material and the lamination roller is 80 °, the pressure is 2 MPa, the substrate surface temperature is 80 ° C, Lamination was performed under the condition of a transfer speed of 2.0 m / min. At this time, the wettability of the photosensitive resin layer on the surface of the substrate was good, and no air bubbles were mixed between the substrate and the photosensitive resin layer.

Subsequently, a color filter was manufactured according to the following procedure. That is, the support was removed by peeling off at the interface between the support and the thermoplastic resin layer, and the photosensitive resin layer (R) was transferred onto a glass substrate. In this state, a photosensitive resin layer (R), an oxygen blocking layer, and a thermoplastic resin layer are laminated in this order on a glass substrate.

[Exposure and Developing Steps] Next, a predetermined photomask is arranged above the thermoplastic resin layer as the outermost layer, and exposure is performed through the photomask with an ultra-high pressure mercury lamp under the conditions shown in Table 2 below. did. After that, the transer treatment liquid TP
Using a 10-fold dilution (33 ° C.) of D-1 (manufactured by Fuji Photo Film Co., Ltd.), the thermoplastic resin layer and the intermediate layer were removed by shower development (development treatment 1). At this stage, the photosensitive resin layer has not been substantially developed. Subsequently, Transer treatment solution T-CD-1 (Fuji Photo Film Co., Ltd.)
Shower development using a 5-fold dilution (33 ° C.)
Unnecessary portions (uncured portions) of the photosensitive resin layer (R) were removed by development [development process 2]. Furthermore, the transer treatment solution T-SD-1
(Fuji Photo Film Co., Ltd.) 10-fold diluted solution (33
C.) was sprayed on the photosensitive resin layer with a shower, and the residue of the uncured portion was completely removed by rubbing with an acrylic roll brush [Development treatment 3]. Table 2 shows the conditions for the development processing.

After the development processing, the substrate was washed with ultrapure water for 60 seconds, drained with an air knife, and further post-baked in a convection oven to form an R on a glass substrate.
A pixel pattern was formed. Table 2 below shows the conditions of the post-baking.

[0114]

[Table 2]

Next, after using a photosensitive resin material for forming a green (G) pixel and removing the protective film, the same operation as in the case of forming the R pixel is repeated (a substrate surface temperature of 80 ° C.).
C), transferring the photosensitive resin layer (G) covering the R pixel pattern, exposing it using a predetermined photomask under the conditions shown in Table 2, and further developing and post-baking the G pixel comprising the G layer. A pattern was formed. At this time, irregularities due to the R pixel pattern are present on the surface to which the photosensitive resin layer (G) is transferred, but transfer is performed without mixing of air bubbles between the substrate and the photosensitive resin layer (G). As a result, a G pixel pattern having no pixel defects could be formed on the substrate. As described above, a work-in-progress of a color filter composed of R pixels and G pixels was obtained.

Example 2 A substrate surface (silane-coupling-treated) was used in the same manner as in Example 1 (substrate surface temperature: 80 ° C.), except that the following substrate was used instead of the substrate prepared in Example 1. The photosensitive resin layer (R) was transferred onto the surface on the other side. In this state, the photosensitive resin layer is placed on the glass substrate.
(R), an oxygen barrier layer, and a thermoplastic resin layer are laminated in this order. At this time, the wettability of the photosensitive resin layer on the surface of the substrate was good, and no air bubbles were mixed between the substrate and the photosensitive resin layer.

[Preparation of Substrate] A silane coupling agent (K) was applied to the surface of an H-coated glass substrate (manufactured by Nippon Sheet Glass Co., Ltd.).
A 10% aqueous solution of BM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) was coated to obtain a substrate having a polar component of surface free energy of 22 dyne / cm (surface temperature of 25 ° C.) on the coated surface.

Subsequently, the same operation as in Example 1 was performed to form an R pixel pattern.
(G) A photosensitive resin layer (G) was formed in the same manner as in Example 1 (substrate surface temperature: 80 ° C.) using a photosensitive resin material for pixel formation.
Was transferred to form a G pixel pattern. At this time, irregularities due to the R pixel pattern are present on the surface to which the photosensitive resin layer (G) is transferred, but transfer is performed without mixing of air bubbles between the substrate and the photosensitive resin layer (G). I was able to. Further, a G pixel pattern having no pixel defect was formed on the substrate. As described above, a work-in-progress of a color filter composed of R pixels and G pixels was obtained.

Comparative Example 1 An uncoated H-coated glass substrate (Nippon Sheet Glass Co., Ltd.) was used instead of the substrate prepared in Example 1.
Polar component of surface free energy = 42 dyne / c
m (surface temperature: 25 ° C.) and 44 dyne / cm (surface temperature: 60 ° C.), except that the photosensitive resin layer (R) was formed on the surface of the substrate in the same manner as in Example 1 (substrate surface temperature: 80 ° C.).
Was transcribed. At this time, air bubbles were observed between the substrate and the photosensitive resin layer.

Subsequently, the same operation as in Example 1 was performed to form an R pixel pattern.
(G) A photosensitive resin layer (G) was formed in the same manner as in Example 1 (substrate surface temperature: 80 ° C.) using a photosensitive resin material for pixel formation.
Was transferred to form a G pixel pattern. At this time, irregularities due to the R pixel pattern exist on the surface to which the photosensitive resin layer (G) is transferred. However, transfer cannot be performed on the irregular surface without mixing of air bubbles. A G pixel pattern without pixel defects could not be formed. From the above, a work-in-progress of the color filter of the comparative example including the R pixels and the G pixels was obtained.

[0121]

According to the present invention, it is possible to suppress the generation of bubbles at the time of transfer by the lamination method, and to form a high-precision, low-cost resin laminate without defects and at high speed and stably. A method for producing a body can be provided. Further, the method for producing a resin laminate of the present invention can provide a high-definition color filter which is obtained at low cost and has no pixel defects (white spots).

[Brief description of the drawings]

FIG. 1A is a schematic view for explaining a state in which a photosensitive resin layer is laminated on a substrate in a method for producing a resin laminate of the present invention, and FIG. FIG. 3 is a schematic diagram for explaining a state in which is laminated on a substrate.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Photosensitive resin layer 3 ... Photosensitive resin material

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/26 501 G03F 7/26 501 F term (Reference) 2H025 AA00 AB11 AB13 AC01 AD01 DA19 EA01 EA08 FA03 FA17 2H048 BA43 BA47 BA48 BB37 BB42 2H096 AA28 BA05 CA01 CA02 CA16 CA20 EA02 GA08 JA02 LA16 4D075 AC43 AC99 CA47 CB07 DA04 DA06 DB13 DB36 DB39 DB42 DB43 DB47 DB48 DB50 DC24 EA21 EA45 EB20 EB22 EB24 EB33 EB00 EB33 EB33 EB35 EB33 EB35 EB35 EB35 EB35 EB35 EB35 EB35 EB38 EB35 EB35 EB35 EB38 EB35 EB35 EB35 EB38 EB35 EB35 EB35 EB35 EB35 EB38 EB35 EB35 EB35 EB35 AK35 AK25J AK80 AL01 AL05 AR00A BA02 BA05 EC042 EG002 EH012 EJ082 EJ542 EJ912 GB41 JB14B JB20A JB20B JL00 YY00A YY00B

Claims (5)

[Claims] 1. A method according to claim 1, wherein the protective film is removed from a photosensitive resin material having a photosensitive resin layer and a protective film on a support, and the photosensitive resin layer of the photosensitive resin material is laminated on the surface of the substrate. A method of manufacturing a resin laminate including a step of transferring a photosensitive resin layer onto the substrate by peeling the support after lamination, wherein a surface free energy at the time of lamination of at least a surface of the substrate to be transferred is obtained. Is 35 dy
Ne / cm or less. 2. The method according to claim 1, wherein the protective film is removed from a photosensitive resin material having a photosensitive resin layer and a protective film on a support, and the photosensitive resin layer of the photosensitive resin material is laminated on the surface of the substrate. A method of manufacturing a resin laminate including a step of transferring a photosensitive resin layer onto the substrate by peeling the support after lamination, wherein the surface free energy of at least the surface of the substrate to be transferred, at the time of lamination, 35dyne polar component
/ Cm or less, and then laminating and laminating a photosensitive resin layer on the surface. 3. The method for producing a resin laminate according to claim 1, wherein a polar component of surface free energy is 35 dyne / cm or less and a dispersion component of surface free energy is 40 dyne / cm or less during lamination. 4. The surface free energy of the photosensitive resin layer of the photosensitive resin material at the time of lamination is 50 d.
The method for producing a resin laminate according to any one of claims 1 to 3, which is not more than yne / cm. 5. A color filter obtained by the method for producing a resin laminate according to any one of claims 1 to 4.