Plastic container containing resin composition

Abstract

To provide a plastic container containing a resin composition that has good agitation of the resin composition in the plastic container and does not cause deterioration of the plastic container or peeling of the container label.SOLUTION: The present invention relates to a plastic container containing a resin composition, wherein the volume ratio of the resin composition is between 30 vol% or more and 80 vol% or less of the volume of the plastic container, and the resin composition contains at least one organic solvent selected from the group consisting of ester-based hydrocarbons having a glycol skeleton, alcohol-based hydrocarbons having a glycol skeleton, and ether-based hydrocarbons having a glycol skeleton.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a plastic container containing a resin composition.

Background Art

[0002] Various resin compositions are usually stored in containers until use. Examples of the resin composition include a solder resist composition for a printed wiring board, an etching resist composition for copper, stainless steel, a glass substrate, etc., a plating resist composition for metal, ceramic, plastic, etc., a resin for forming a decorative part of a touch panel, a thermosetting resin composition for filling through holes, and the like.

[0003] For example, as a solder resist for a printed wiring board, a liquid curable resin composition (ink) that can form an image by applying, exposing, and developing on a substrate and heating and curing to form a coating film is used.

[0004] The curable resin composition includes a one-component type in which one liquid is contained in one container, or a two-component type in which two liquids are contained in separate containers and mixed before use from the viewpoint of storage stability (for example, Patent Document 1, etc.). The curable resin composition is applied to a printed circuit board after being stirred into a uniform composition before use, regardless of whether a one-component type or a two-component type composition is used.

[0005] Conventionally, metal containers have been used to store resin compositions. In recent years, plastic containers (especially polyolefin containers) have been widely used from the viewpoints of weight reduction, cost reduction, airtightness, etc.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] In the current situation as described in the above background art, when stirring the liquid resin composition in a container before use, if the filling amount of the composition in the container is too much, it will overflow from the container during stirring. On the other hand, if it is too little, the composition will adhere to the stirring blades, the inner wall of the container, etc., resulting in insufficient stirring, and problems such as concentration imbalance of each component in the composition will occur, and it has been found that the stirring efficiency of the composition in the container decreases.

[0008]

[0007] Also, when storing a liquid resin composition in a plastic container (especially a polyolefin container) (including the case of temporarily storing the composition after stirring it before use), the organic solvent in the composition may interact with the material of the plastic container, resulting in deterioration of the container or peeling of the label attached to the outer surface of the container containing the composition.

[0009] In view of the above problems, an object of the present invention is to provide a plastic container containing a resin composition that has good stirrability in a plastic container and does not cause deterioration of the plastic container or peeling of the container label.

Means for Solving the Problems

[0010] As a result of intensive studies, the inventor has found that by adjusting the filling rate of the resin composition into the container within a predetermined range and setting a predetermined combination of the material of the plastic container and the components (especially organic solvents) contained in the resin composition, the above problems can be solved. Based on such findings, further studies were carried out to complete the present invention.

[0011]

[0008] That is, the present invention provides a plastic container containing the following resin composition. Item 1. A plastic container containing a resin composition, wherein the volume ratio of the resin composition is 30 vol% or more and 80 vol% or less with respect to the volume of the plastic container, and the resin composition contains at least one organic solvent selected from the group consisting of ester-based hydrocarbons having a glycol skeleton, alcohol-based hydrocarbons having a glycol skeleton, and ether-based hydrocarbons having a glycol skeleton. A plastic container containing a resin composition. Item 2. The plastic container according to Item 1, wherein the material of the plastic container is a polyolefin resin. Item 3. The ester-based hydrocarbon having a glycol skeleton is an ester of a polyalkylene glycol monoalkyl ether and a carboxylic acid compound, the alcohol-based hydrocarbon having a glycol skeleton is a polyalkylene glycol monoalkyl ether, and the ether-based hydrocarbon having a glycol skeleton is a polyalkylene glycol dialkyl ether. A plastic container containing the resin composition according to Item 1 or 2. Item 4. The thickness of the plastic of the plastic container is 1 mm or more and 10 mm or less. A plastic container containing the resin composition according to any one of Items 1 to 3. Item 5. The shape of the plastic container is cylindrical (columnar). A plastic container containing the resin composition according to any one of Items 1 to 4. Item 6. The volume of the plastic container is 0.1 L or more and 20 L or less. A plastic container containing the resin composition according to any one of Items 1 to 5. Item 7. The viscosity of the resin composition at 5 rpm at 25°C is 0.1 dPa·s or more and 2,000 dPa·s or less. A plastic container containing the resin composition according to any one of Items 1 to 6. Item 8. The resin composition is a developable curable resin composition, a heat-drying type resin composition, or a thermosetting resin composition. A plastic container containing the resin composition according to any one of Items 1 to 7. Item 9. The plastic container according to Item 8, wherein the resin composition is a developable resin composition. Item 10. A plastic container containing the resin composition according to Item 8, wherein the resin composition is a heat-drying type resin composition. Item 11. A plastic container containing the resin composition according to Item 8, wherein the resin composition is a thermosetting resin composition. In this specification, when a numerical range is expressed using "~" as in "A~B", unless otherwise specified, this means "A or more and B or less".

Advantages of the Invention

[0012] The plastic container containing the resin composition of the present invention has good stirrability of the resin composition in the plastic container. Further, deterioration of the plastic container (especially a polyolefin container) and peeling of the label on the container surface are less likely to occur.

Embodiments for Carrying Out the Invention

[0013] Hereinafter, a plastic container containing the resin composition according to the present embodiment will be described.

[0014] The plastic container containing the resin composition of the present invention has a volume ratio of the resin composition of 30 vol% or more and 80 vol% or less with respect to the volume of the plastic container, and the resin composition contains at least one organic solvent selected from the group consisting of an ester-based hydrocarbon having a glycol skeleton, an alcohol-based hydrocarbon having a glycol skeleton, and an ether-based hydrocarbon having a glycol skeleton.

[0015] (1) Plastic container Examples of the material of the plastic container include polyolefin resins from the viewpoints of versatility, processability, cost, airtightness, etc. The plastic container is usually composed of members such as a container body, a cap (lid), a stopper (inner stopper, etc.). It is preferable that the materials of these members are all polyolefin resins. Examples of the polyolefin resin include polyethylene, polypropylene, and copolymers containing these as partial structures.

[0016] Examples of polyethylene include high-density polyethylene (HDPE: specific gravity 0.92 to 0.96, heat distortion temperature 130°C or lower), low-density polyethylene (LDPE: specific gravity 0.91 to 0.92, heat distortion temperature 100°C or lower), very low-density polyethylene (VLDPE or ULDPE: specific gravity < 0.9), linear low-density polyethylene (LLDPE: specific gravity < 0.94), ultra-high molecular weight polyethylene (UHMW-PE: generally having a molecular weight of 1.5 million or more), and the like.

[0017] Examples of polypropylene include isotactic polypropylene, syndiotactic polypropylene, and atactic polypropylene, depending on the difference in stereoregularity.

[0018] Examples of copolymers having polyethylene and / or polypropylene as a partial structure include ethylene vinyl acetate copolymer (EVA), ethylene ethyl acrylate copolymer (EEA), and the like.

[0019] One or more of the above polyolefin resins can be selected. Among them, polyethylene or polypropylene is preferred.

[0020] The shape of the plastic container is not particularly limited as long as it is easy to handle and can stir the resin composition inside the container. For example, a cylindrical shape (cylindrical), a square prism shape, etc. can be mentioned. From the viewpoint of easy stirring of the resin composition inside the container, a cylindrical shape is preferred.

[0021] The thickness of the plastic container (the thickness of the container wall) can be set within a desired range in consideration of the strength, weight, etc. of the container. For example, 1 mm or more and 10 mm or less is preferred, 1 mm or more and 8 mm or less is more preferred, 2 mm or more and 6 mm or less is further preferred, and 2 mm or more and 5 mm or less is particularly preferred. When the thickness is 1 mm or more, the strength is maintained and it is difficult to deform when handling the plastic container. When the thickness is 10 mm or less, the container does not become too heavy and there is no problem in transportation.

[0022] The capacity (net content) of the plastic container can be set within a desired range in consideration of the stirrability, weight, ease of handling, etc. of the resin composition. For example, it is preferably 0.1 L or more and 20 L or less, more preferably 0.3 L or more and 18 L, and even more preferably 0.5 L or more and 15 L or less. If the capacity is 0.1 L or more, the stirrability of the resin composition is good, and the remaining amount (loss amount) due to adhesion to the inside of the container or the stirring blades can be reduced. If it is 20 L or less, the container is less likely to deform, the container weight does not become too heavy, and there is no problem in transportation.

[0023] When the plastic container is cylindrical, the ratio (diameter / height) of the diameter of the inner bottom surface to the inner height of the cylinder is not particularly limited, and examples thereof include 0.1 to 1.5, preferably 0.3 to 1.3.

[0024] (2) Resin composition The resin composition contained in the plastic container is characterized by containing at least one organic solvent selected from the group consisting of ester-based hydrocarbons having a glycol skeleton, alcohol-based hydrocarbons having a glycol skeleton, and ether-based hydrocarbons having a glycol skeleton. From the viewpoints of coatability, drying property, etc., these organic solvents usually preferably have a boiling point of 80°C or higher, and more preferably 100°C or higher and 250°C or lower. Further, the solubility parameter (SP value) of these organic solvents is usually preferably 8.0 to 15.0, and more preferably 8.5 to 14.5.

[0025] By using such an organic solvent, the interaction with the above plastic container (especially a plastic container made of a polyolefin-based resin) is small, so problems such as deterioration of the container (deformation, softening, etc.) caused by the organic solvent and peeling of labels (seals) etc. attached to the container surface due to bleeding of the organic solvent from the container do not occur.

[0026] Examples of ester hydrocarbons having a glycol skeleton include esters of polyalkylene glycol monoalkyl ethers and carboxylic acid compounds. Examples of the polyalkylene glycol monoalkyl ether include diethylene glycol mono(C1-C6 alkyl) ether, triethylene glycol mono(C1-C6 alkyl) ether, dipropylene glycol mono(C1-C6 alkyl) ether, tripropylene glycol mono(C1-C6 alkyl) ether, and the like. Examples of the carboxylic acid compound include C1-C6 carboxylic acid compounds such as formic acid, acetic acid, and propionic acid, and preferably C2 or C3 carboxylic acid compounds. Specific examples of the ester of the polyalkylene glycol monoalkyl ether and the carboxylic acid compound include diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate (boiling point 217 °C), dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and the like. Diethylene glycol monomethyl ether acetate is preferred.

[0027] Examples of alcohol hydrocarbons having a glycol skeleton include polyalkylene glycol monoalkyl ethers and the like. Examples of the polyalkylene glycol monoalkyl ether include diethylene glycol mono(C1-C6 alkyl) ether, triethylene glycol mono(C1-C6 alkyl) ether, dipropylene glycol mono(C1-C6 alkyl) ether, tripropylene glycol mono(C1-C6 alkyl) ether, and the like. Specifically, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether (boiling point 188 °C), dipropylene glycol monoethyl ether, and the like can be mentioned. Dipropylene glycol monomethyl ether is preferred.

[0028] Examples of the ether-based hydrocarbon having a glycol skeleton include polyalkylene glycol dialkyl ethers. Examples of the polyalkylene glycol dialkyl ether include diethylene glycol di(C1-C6 alkyl) ether, triethylene glycol di(C1-C6 alkyl) ether, dipropylene glycol di(C1-C6 alkyl) ether, tripropylene glycol di(C1-C6 alkyl) ether, and the like. Specifically, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether (boiling point 177 ° C), dipropylene glycol diethyl ether, and the like can be mentioned. Preferably, it is dipropylene glycol dimethyl ether.

[0029] The resin composition contained in the plastic container contains the above organic solvent and a resin such as a carboxyl group-containing resin described later, and may contain other components as necessary.

[0030] The storage form of the resin composition may be either a form contained in one container (one-component type) or a form contained in two containers (two-component type). In this specification, the "plastic container containing the resin composition" means, in the one-component type, the plastic container containing the resin composition, and in the two-component type, the plastic container containing the resin composition after mixing one liquid with the other liquid.

[0031] The resin composition is in a liquid state and is applied to various substrates after being stirred in a plastic container. Whether the resin composition is of the one-component type or the two-component type, before being applied to a substrate or the like, it is prepared as a uniform resin composition that has been sufficiently mixed and stirred to eliminate the concentration imbalance of each component. In the one-component type, the resin composition can be stirred in the container containing the resin composition, and in the two-component type, the two liquids can be mixed and stirred in one container.

[0032] When stirring a resin composition in a plastic container, it can be stirred using a stirrer. For example, a stirrer having rotating blades can be used. The size of the rotating blades can be selected according to the shape and size of the container. The diameter of the rotating blades is usually 20 mm or more and 600 mm or less, preferably 40 mm or more and 300 mm or less, and more preferably 50 mm or more and 200 mm or less. The rotation speed is usually 100 rpm or more and 1,000 rpm or less, preferably 200 rpm or more and 900 rpm or less, and more preferably 300 rpm or more and 800 rpm or less. The temperature of the resin composition during stirring is usually 5°C or more and 40°C or less, preferably 10°C or more and 30°C or less, and more preferably 15°C or more and 25°C or less. The stirring time is usually 1 minute or more and 30 minutes or less, preferably 2 minutes or more and 10 minutes or less.

[0033] The ratio of the resin composition contained in the plastic container is such that the volume ratio of the resin composition is in the range of 30 vol% or more and 80 vol% or less, preferably in the range of 35 vol% or more and 75 vol% or less, and more preferably in the range of 40 vol% or more and 70 vol% or less, with respect to the volume of the plastic container. Thereby, it is possible to prevent the resin composition from overflowing from the plastic container during stirring, or to reduce the remaining amount (loss amount) of the resin composition remaining in the container or adhering to the stirring blades during stirring. This volume ratio means the volume ratio of the resin composition in the plastic container in the case of a one-component type, and means the volume ratio of the resin composition in the container after the mixed resin composition is contained in one plastic container in the case of a two-component type. Also, this volume ratio is usually a value calculated from the volume of the plastic container and the volume of the resin composition at 10 to 30°C (particularly 22°C).

[0034] The viscosity of the resin composition contained in a plastic container at 25°C and at a rotational speed of 5 rpm is, for example, in the range of 0.1 dPa·s or more and 2,000 dPa·s or less, preferably in the range of 30 dPa·s or more and 1,000 dPa·s or less, more preferably in the range of 60 dPa·s or more and 500 dPa·s or less, and even more preferably in the range of 90 dPa·s or more and 200 dPa·s or less. The viscosity of this resin composition, in the case of a one-component type, means the viscosity of the resin composition in the plastic container, and in the case of a two-component type, means the viscosity of the resin composition in the container after the mixed resin composition is contained in one plastic container.

[0035] The viscosity of the resin composition shall be measured using a cone-and-plate viscometer (manufactured by Toki Sangyo Co., Ltd., TVE-33H, rotor 3°×R9.7) in accordance with JIS-Z8803:2011, specifically, item 10 "Measurement method of viscosity by a cone-and-plate rotational viscometer" of JIS-Z8803:2011. The viscosity shall be the 30-second value measured under the conditions of 25°C and a rotor rotational speed of 5.0 rpm. Hereinafter, the value of the viscosity of the resin composition in this specification is the value obtained using this method.

[0036] The resin composition contained in a plastic container is not particularly limited as long as it contains the above-mentioned organic solvent and resin. Typical examples thereof include a developable curable resin composition used for a solder resist of a printed wiring board; a heat-drying type resin composition (for example, an etching resist composition for copper, stainless steel, glass substrates, etc., a plating resist composition for metals, ceramics, plastics, etc.); a thermosetting resin composition (for example, a composition for forming a decorative part on a glass substrate, a composition for filling a through hole, etc.). Hereinafter, each will be described.

[0037] <Developable curable resin composition> Examples of the developable curable resin composition used for a solder resist of a printed wiring board include, but are not limited to, the following compositions.

[0038] Examples of the developable curable resin composition include those containing at least a photopolymerizable monomer and a thermosetting component, and may further contain a photopolymerization initiator, a sensitizer, a thermosetting catalyst, an inorganic filler, a colorant, an organic solvent, etc. When the storage form of the developable curable resin composition is a one-component type, the above components are contained in one container. When the storage form is a two-component type, the above components are divided into Agent A and Agent B, and each is contained in two containers. It is common to use a two-component type from the viewpoint of storage stability. In the case of a two-component type, Agent A contains at least a resin containing a carboxyl group, and may further contain a photopolymerizable monomer, a photopolymerization initiator, a sensitizer, a thermosetting catalyst, an inorganic filler, a colorant, an organic solvent, etc. Agent B contains at least a thermosetting component, and may further contain a photopolymerizable monomer, a photopolymerization initiator, a thermosetting catalyst, an inorganic filler, an organic solvent, etc.

[0039] The developable curable resin composition may be prepared from either a one-component type or a two-component type. The viscosity of the developable curable resin composition at 25 °C and 5 rpm after preparation is, for example, in the range of 0.1 dPa·s or more and 2,000 dPa·s or less, preferably in the range of 30 dPa·s or more and 1,000 dPa·s or less, more preferably in the range of 60 dPa·s or more and 500 dPa·s or less, and even more preferably in the range of 90 dPa·s or more and 400 dPa·s or less.

[0040] When the developable curable resin composition is of the two-component type, the viscosity of Agent A at 25 °C and 5 rpm is, for example, in the range of 50 dPa·s or more and 500 dPa·s or less, preferably in the range of 70 dPa·s or more and 400 dPa·s or less, and more preferably in the range of 100 dPa·s or more and 400 dPa·s or less.

[0041] The viscosity of Agent B at 25 °C and 5 rpm is, for example, in the range of 30 dPa·s or more and 300 dPa·s or less, preferably in the range of 50 dPa·s or more and 150 dPa·s or less, and more preferably in the range of 70 dPa·s or more and 100 dPa·s or less.

[0042] With respect to the total amount of Agent A and Agent B, the mixing ratio of Agent A is 75% by mass or more and less than 100% by mass, preferably 77% by mass or more and 97% by mass or less, more preferably 80% by mass or more and 95% by mass or less, and the mixing ratio of Agent B is more than 0% by mass and 25% by mass or less, preferably 3% by mass or more and 23% by mass or less, preferably 5% by mass or more and 20% by mass or less.

[0043] If the mixing ratio of Agent A and Agent B is within the above range, the volume ratio of Agent B decreases, and as a result, the packaging property is improved.

[0044] The degree of dispersion in the grind gauge after mixing Agent A and Agent B is usually 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less.

[0045] The degree of dispersion in the grind gauge shall be measured by the granular method using a grind gauge with a width of 90 mm, a length of 240 mm, and a maximum depth of 50 μm in accordance with JIS K 5600-2-5:1999 "Part 2 - Section 5: Degree of Dispersion". The granular method is specifically as follows. That is, observe the point at which distinct spots begin to appear on the product (sample to be measured). In particular, observe the point where 5 to 10 particles are included in a 3 mm-wide band along the groove. Ignore the sparse spots that appear before the point where distinct spots begin to appear.

[0046] When the developable curable resin composition is of the two-component type, the viscosity of Agent B at 5 rpm at 25 °C is preferably lower than that of Agent A. The low viscosity of Agent B improves the fluidity during filling and is excellent in workability and productivity.

[0047] Hereinafter, taking the case where the developable curable resin composition is of the two-component type as a typical example, the components constituting Agent A and Agent B will be described. However, the description of these components also applies to the description of the components when the developable curable resin composition is of the one-component type.

[0048] [Components Constituting Agent A] [Resin Containing Carboxyl Group] As the carboxyl group-containing resin, various conventionally known resins having a carboxyl group in the molecule can be used. By including a carboxyl group-containing resin in the curable resin composition, the curable resin composition can be imparted with alkali developability. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable in terms of photocurability and developability resistance. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or their derivatives. When only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used, in order to make the composition photocurable, it is necessary to use in combination a compound having a plurality of ethylenically unsaturated groups in the molecule, that is, a photopolymerizable monomer, which will be described later. Specific examples of the carboxyl group-containing resin can include the following compounds (either oligomers or polymers may be used).

[0049] (1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc.

[0050] (2) A carboxyl group-containing urethane resin by the polyaddition reaction of a diisocyanate such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc. with a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid, dimethylolbutanoic acid and a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

[0051] (3) A carboxyl group-containing photosensitive urethane resin obtained by the polyaddition reaction of diisocyanate with (meth)acrylate of a bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, or a partially acid anhydride-modified product thereof, a carboxyl group-containing diol compound, and a diol compound.

[0052] (4) A carboxyl group-containing photosensitive urethane resin having a terminal (meth)acrylated structure, obtained by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, during the synthesis of the resin of (2) or (3).

[0053] (5) A carboxyl group-containing photosensitive urethane resin having a terminal (meth)acrylated structure, obtained by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin of (2) or (3).

[0054] (6) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl groups present in the side chain.

[0055] (7) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl groups of a bifunctional (solid) epoxy resin with epichlorohydrin with (meth)acrylic acid and adding a dibasic acid anhydride to the resulting hydroxyl groups.

[0056] (8) A carboxyl group-containing polyester resin obtained by reacting a bifunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride to the resulting primary hydroxyl groups.

[0057] (9) A carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound having a plurality of epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid, and then reacting a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. with respect to the alcoholic hydroxyl group of the obtained reaction product.

[0058] (10) A carboxyl group-containing photosensitive resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide, propylene oxide, etc., then reacting an unsaturated group-containing monocarboxylic acid with the obtained reaction product, and then reacting a polybasic acid anhydride with the obtained reaction product.

[0059] (11) A carboxyl group-containing photosensitive resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate, propylene carbonate, etc., then reacting an unsaturated group-containing monocarboxylic acid with the obtained reaction product, and then reacting a polybasic acid anhydride with the obtained reaction product.

[0060] (12) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resin of the above (1) to (11).

[0061] In this specification, (meth)acrylate is a general term for acrylate, methacrylate and their mixtures, and the same applies to other similar expressions.

[0062] The carboxyl group-containing resin that can be used in the present invention is not limited to those listed above. Also, the above-listed carboxyl group-containing resins may be used alone or in combination of multiple types.

[0063] In the present invention, considering the developability when using a weak alkaline developer such as an aqueous sodium carbonate solution and the drawability of the resist pattern, the acid value of the carboxyl group-containing resin is preferably in the range of 30 to 150 mgKOH / g, and more preferably in the range of 50 to 120 mgKOH / g. Although the developability improves as the acid value of the carboxyl group-containing resin increases, since the dissolution of the exposed portion by the developer progresses, there may be a case where it is dissolved and peeled off with the developer without distinction between the exposed portion and the unexposed portion.

[0064] The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but generally it is in the range of 2,000 to 150,000, and preferably in the range of 3,000 to 100,000. By using a carboxyl group-containing resin having a weight average molecular weight of 2,000 or more, the resolution and tack-free performance can be improved. Also, by using a carboxyl group-containing resin having a weight average molecular weight of 150,000 or less, the developability and storage stability can be improved. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

[0065] The content of the carboxyl group-containing resin in Agent A can be appropriately set according to the viscosity of the target Agent A. The content of the carboxyl group-containing resin in Agent A is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, in the total amount of Agent A in terms of solid content.

[0066] Also, the content of the carboxyl group-containing resin in the developable curable resin composition (which means a one-component composition or a composition obtained by mixing a two-component Agent A and Agent B. The same applies hereinafter) can be appropriately set according to the viscosity of the target developable curable resin composition. The content of the carboxyl group-containing resin in the developable curable resin composition is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, in the total amount of the composition in terms of solid content.

[0067] [Components constituting Agent B] [Thermosetting component] As the thermosetting component, any known one can be used. When the developable curable resin composition contains a thermosetting component, the heat resistance of the cured film can be improved. Examples of the thermosetting component include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives; isocyanate compounds; blocked isocyanate compounds; cyclo carbonate compounds; epoxy compounds; oxetane compounds; episulfide resins; bismaleimides; carbodiimide resins; and other known thermosetting components. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio)ether groups) in the molecule. The thermosetting component can be used alone or in combination of two or more.

[0068] The thermosetting component having a plurality of cyclic (thio)ether groups in the above molecule is a compound having a plurality of 3-, 4- or 5-membered cyclic (thio)ether groups in the molecule. Examples include compounds having a plurality of epoxy groups in the molecule, that is, polyfunctional epoxy compounds; compounds having a plurality of oxetanyl groups in the molecule, that is, polyfunctional oxetane compounds; compounds having a plurality of thioether groups in the molecule, that is, episulfide resins, etc. Particularly preferred are polyfunctional epoxy compounds.

[0069] Examples of such polyfunctional epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, novolac type epoxy resin of bisphenol A, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, etc.

[0070] Examples of commercially available epoxy resins include jER 828, 806, 807, YX8000, YX8034, 834 manufactured by Mitsubishi Chemical Corporation, YD-128, YDF-170, ZX-1059, ST-3000 manufactured by Nippon Steel Chemical & Material Co., Ltd., EPICLON 830, 835, 840, 850, N-730A, N-695 manufactured by DIC Corporation, RE-306 manufactured by Nippon Kayaku Co., Ltd., and the like.

[0071] Examples of polyfunctional oxetane compounds include polyfunctional oxetanes such as bis[(3-methyl-3-oxetanylmethoxy)methyl] ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl] ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, and their oligomers or copolymers. In addition, etherified products of oxetane alcohol with resins having hydroxyl groups such as novolak resins, poly(p-hydroxystyrene), calixarene-based bisphenols, calixarenes, calixresorcinarenes, or silsesquioxane, and the like can also be mentioned. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth)acrylates.

[0072] Examples of compounds having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resins and the like. Also, using the same synthesis method, episulfide resins obtained by replacing the oxygen atom of the epoxy group of novolak type epoxy resins with a sulfur atom can also be used.

[0073] Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.

[0074] As the isocyanate compound, a polyisocyanate compound can be blended. Examples of the polyisocyanate compound include aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, and 2,4-tolylene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate), and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; and adducts, biuret bodies, and isocyanurate bodies of the isocyanate compounds mentioned above.

[0075] As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound that can react with the isocyanate blocking agent include, for example, the above-mentioned polyisocyanate compounds. Examples of the isocyanate blocking agent include phenolic blocking agents; lactam-based blocking agents; active methylene-based blocking agents; alcohol-based blocking agents; oxime-based blocking agents; mercaptan-based blocking agents; acid amide-based blocking agents; imide-based blocking agents; amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents, and the like.

[0076] The content of the thermosetting component in Agent B can be appropriately set according to the target viscosity of Agent B. The content of the thermosetting component in Agent B is preferably 20 to 100% by mass, more preferably 25 to 80% by mass, in terms of solid content in the total amount of Agent B.

[0077] The content rate of the thermosetting component in the developable curable resin composition can be appropriately set according to the viscosity of the intended developable curable resin composition. The content rate of the thermosetting component in the developable curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 20% by mass in the total amount of the composition in terms of solid content.

[0078] [Component that may be contained in at least one of Agent A and Agent B] [Photoinitiator] The photoinitiator is for reacting a carboxyl group-containing resin or a photopolymerizable monomer by exposure. Any known photoinitiator can be used. The photoinitiator may be used alone or in combination of two or more.

[0079] As the photoinitiator, specifically, for example, bisacylphosphine oxides such as bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; monoacylphosphine oxides such as 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, methyl 2,4,6-trimethylbenzoylphenylphosphinate, 2-methylbenzoyldiphenylphosphine oxide, isopropyl pivaloylphenylphosphinate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; hydroxyacetophenones such as ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methyl benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone;Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone; Thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; Ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, ethyl p-dimethylbenzoate; Oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetoxyoxime); Titanocenes such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyr-1-yl)ethyl)phenyl]titanium; Phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. can be mentioned.;

[0080] Examples of commercially available α-aminoacetophenone-based photoinitiators include Omnirad 907, 369, 369E, 379, etc. manufactured by IGM Resins. Examples of commercially available acylphosphine oxide-based photoinitiators include Omnirad TPO H, 819, etc. manufactured by IGM Resins. Examples of commercially available oxime ester-based photoinitiators include Irgacure OXE01, OXE02 manufactured by BASF Japan Ltd., N-1919 manufactured by ADEKA Corporation, Adeka Arcles NCI-831, NCI-831E, TR-PBG-304 manufactured by Changzhou Strong Electronic New Materials Co., Ltd., and the like.

[0081] In addition, examples include carbazole oxime ester compounds described in JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-T-2008-509967, JP-T-2009-040762, JP-A-2011-80036, and the like.

[0082] The content of the photoinitiator in Agent A can be appropriately set so that the photosensitivity required for the dried coating film of the resin composition obtained by mixing Agent A and Agent B can be obtained. When the photoinitiator is contained in Agent A, the content is preferably more than 0% by mass and 20% by mass or less, more preferably 0.5 to 10% by mass, in terms of solid content based on the total amount of Agent A. When the photoinitiator is contained in Agent B, the content can be appropriately set so that the photosensitivity required for the dried coating film of the resin composition obtained by mixing Agent A and Agent B can be obtained. The content of the photoinitiator in Agent B is preferably more than 0% by mass and 20% by mass or less, more preferably 0 to 10% by mass, in terms of solid content based on the total amount of Agent B. Furthermore, when a photopolymerization initiator is included in the developable curable resin composition, its content is preferably more than 0% by mass and 20% by mass or less, more preferably 0.5 - 10% by mass in terms of solid content based on the total amount of the composition. When the content of the photopolymerization initiator in the developable curable resin composition exceeds 0% by mass, the photocurability of the developable curable resin composition becomes good, and the film properties such as chemical resistance also become good. On the other hand, when it is 20% by mass or less, the light absorption on the surface of the resist film (cured film) becomes good, and the deep part curability is less likely to decrease.

[0083] In combination with the above-mentioned photopolymerization initiator, a photoinitiator aid or a sensitizer may be used. Examples of the photoinitiator aid or sensitizer include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. In particular, it is preferable to use thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone. By including the thioxanthone compound, the deep part curability can be improved. Although these compounds may be used as a photopolymerization initiator in some cases, it is preferable to use them in combination with a photopolymerization initiator. Also, the photoinitiator aid or sensitizer may be used alone or in combination of two or more.

[0084] Note that since these photopolymerization initiators, photoinitiator aids, and sensitizers absorb specific wavelengths, in some cases, the sensitivity becomes low and they may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the resin composition. If necessary, they can absorb light of a specific wavelength to enhance the surface photoreactivity, change the line shape and opening of the resist pattern to vertical, tapered, or reverse tapered, and improve the accuracy of the line width and opening diameter.

[0085] [Photopolymerizable monomer] In the developable curable resin composition, a photopolymerizable monomer can be blended. The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond. Examples of such photopolymerizable monomers include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; mono- or di-(meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; polyvalent (meth) acrylates of polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or their adducts with ethylene oxide or propylene oxide; (meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine (meth) acrylate. The photopolymerizable monomer may be used alone or in combination of two or more kinds.

[0086] The content of the photopolymerizable monomer in Agent A can be appropriately set so that the photosensitivity required for the dried coating film of the resin composition obtained by mixing Agent A and Agent B can be obtained. When the photopolymerizable monomer is contained in Agent A, the content is preferably 0 to 30% by mass, more preferably 0 to 20% by mass in the total amount of Agent A in terms of solid content. Also, when the photopolymerizable monomer is contained in Agent B, the content can be appropriately set so that the photosensitivity required for the dried coating film of the resin composition obtained by mixing Agent A and Agent B can be obtained. When the photopolymerizable monomer is contained in Agent B, the content is preferably more than 0% by mass and 40% by mass or less, more preferably 5 to 35% by mass in the total amount of the composition in terms of solid content. Furthermore, when a photopolymerizable monomer is contained in the developable curable resin composition, its content is preferably more than 0% by mass and 30% by mass or less, more preferably 5 to 20% by mass, in terms of solid content based on the total amount of the composition. When the content of the photopolymerizable monomer in the developable curable resin composition is more than 0% by mass, the photocurability is good, and pattern formation is easy in alkali development after irradiation with active energy rays. On the other hand, when it is 30% by mass or less, halation hardly occurs and good resolution can be obtained.

[0087] [Thermosetting catalyst] A thermosetting catalyst can be blended in the developable curable resin composition. Examples of the thermosetting catalyst include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide, sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Also, commercially available ones include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole-based compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT 3513N (trade name of a dimethylamine-based compound) manufactured by San-Apro Ltd., DBU, DBN, U-CAT SA 102 (all are bicyclic amidine compounds and their salts), etc. In particular, it is not limited to these, and any thermosetting catalyst for epoxy resins or oxetane compounds, or any one that promotes the reaction between at least one of epoxy groups and oxetanyl groups and carboxyl groups may be used, and they may be used alone or in combination of two or more.

[0088] Furthermore, S-triazine derivatives such as guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct can also be used. Preferably, a compound that also functions as an adhesion promoter among these is used in combination with a thermosetting catalyst. The thermosetting catalyst may be used alone or in combination of two or more.

[0089] The content of the thermosetting catalyst in Agent A can be appropriately set so that the photosensitivity required for the dried coating film of the resin composition obtained by mixing Agent A and Agent B can be obtained. When the thermosetting catalyst is contained in Agent A, its content is preferably more than 0% by mass and 20% by mass or less, more preferably 1 to 10% by mass in terms of solid content based on the total amount of Agent A. Also, the content of the thermosetting catalyst in Agent B can be appropriately set so that the photosensitivity required for the dried coating film of the resin composition obtained by mixing Agent A and Agent B can be obtained. When the thermosetting catalyst is contained in Agent B, its content is preferably more than 0% by mass and 20% by mass or less, more preferably 1 to 10% by mass in terms of solid content based on the total amount of Agent B. Furthermore, when the thermosetting catalyst is contained in the developable curable resin composition, its content is preferably more than 0% by mass and 20% by mass or less, more preferably 1 to 10% by mass in terms of solid content based on the total amount of the composition. When the content of the thermosetting catalyst in the developable curable resin composition exceeds 0% by mass, it has excellent heat resistance. On the other hand, when it is 20% by mass or less, it leads to an improvement in stability over time.

[0090] [Colorant] A colorant can be blended in the developable curable resin composition. The colorant is not particularly limited, and known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and colorants may be used. However, from the viewpoint of reducing environmental load and having less impact on the human body, it is preferably a colorant that does not contain halogen.

[0091] Examples of red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, etc. Specifically, those with the following Color Index (C.I.; published by The Society of Dyers and Colourists) numbers are included.

[0092] Examples of monoazo red colorants include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, etc. Examples of disazo red colorants include Pigment Red 37, 38, 41, etc. Examples of monoazo lake red colorants include Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68, etc. Examples of benzimidazolone red colorants include Pigment Red 171, 175, 176, 185, 208, etc. Examples of perylene red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224, etc. Examples of diketopyrrolopyrrole red colorants include Pigment Red 254, 255, 264, 270, 272, etc. Examples of condensed azo red colorants include Pigment Red 220, 144, 166, 214, 220, 221, 242, etc. Examples of anthraquinone red colorants include Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207, etc. Examples of quinacridone red colorants include Pigment Red 122, 202, 206, 207, 209, etc.

[0093] Examples of cyan colorants include phthalocyanine-based and anthraquinone-based ones. Pigment-based ones include compounds classified as Pigment, such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60. As dye-based ones, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, etc. can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

[0094] Examples of yellow colorants include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, anthraquinone-based, etc. For example, as anthraquinone-based yellow colorants, Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, etc. can be mentioned. As isoindolinone-based yellow colorants, Pigment Yellow 110, 109, 139, 179, 185, etc. can be mentioned. As condensed azo-based yellow colorants, Pigment Yellow 93, 94, 95, 128, 155, 166, 180, etc. can be mentioned. As benzimidazolone-based yellow colorants, Pigment Yellow 120, 151, 154, 156, 175, 181, etc. can be mentioned. Also, as monoazo-based yellow colorants, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, etc. can be mentioned. Also, as disazo-based yellow colorants, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc. can be mentioned.

[0095] In addition, colorants such as purple, orange, brown, black, and white may be added. Specifically, Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C.I.Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Brown 23, 25, carbon black, titanium oxide, etc. may be mentioned.

[0096] The content of the colorant in Agent A can be appropriately set so that the photosensitivity or appearance required for the dried coating film of the resin composition obtained by mixing Agent A and Agent B can be obtained. When Agent A contains a colorant, the content is preferably more than 0% by mass and 10% by mass or less, more preferably 0.2 to 5% by mass, in terms of solid content in the total amount of Agent A. The content of the colorant in Agent B can be appropriately set so that the photosensitivity or appearance required for the dried coating film of the resin composition obtained by mixing Agent A and Agent B can be obtained. When Agent B contains a colorant, the content is preferably more than 0% by mass and 10% by mass or less, in terms of solid content in the total amount of Agent B. Furthermore, when the developable curable resin composition contains a colorant, the content is preferably more than 0% by mass and 10% by mass or less, more preferably 0.2 to 5% by mass, in terms of solid content in the total amount of the composition.

[0097] [Inorganic filler] In the developable curable resin composition, an inorganic filler can be blended. Examples of the inorganic filler include silica such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, nobleburg silica particles, boehmite, magnesium carbonate, calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, calcium zirconate, and the like. The inorganic filler may be used alone or in combination of two or more. By containing the inorganic filler, the heat resistance can be improved and the variation during coating can be reduced.

[0098] The content of the inorganic filler in Agent A can be appropriately set so that heat resistance, adhesion, etc. required for the dried coating film of the resin composition obtained by mixing Agent A and Agent B can be obtained. When the inorganic filler is contained in Agent A, the content is preferably 10 to 60% by mass, more preferably 20 to 55% by mass, in the total amount of Agent A in terms of solid content. The content of the inorganic filler in Agent B can be appropriately set so that heat resistance, adhesion, etc. required for the dried coating film of the resin composition obtained by mixing Agent A and Agent B can be obtained. When the inorganic filler is contained in Agent B, the content is preferably 0% by mass or more and 70% by mass or less in the total amount of Agent B in terms of solid content. Furthermore, when the developable curable resin composition contains an inorganic filler, the content is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, in the total amount of the composition in terms of solid content.

[0099] [Organic solvent] In the developable curable resin composition, within a range that does not impair the properties, for the purpose of preparing the composition and adjusting the viscosity when coating on a substrate or film, etc., organic solvents other than the above three organic solvents can be contained. As the organic solvents other than the above three organic solvents, for example, known and commonly used organic solvents such as petroleum ether, petroleum naphtha, solvent naphtha and other petroleum-based solvents can be used. These organic solvents may be used alone or in combination of two or more.

[0100] The content rate of the organic solvent in Agent A can be appropriately set according to the viscosity of the target Agent A. The content rate of the organic solvent in Agent A is preferably 10 to 50% by mass, more preferably 15 to 40% by mass in the total amount of Agent A. The content rate of the organic solvent in Agent B can be appropriately set according to the viscosity of the target Agent B. The content rate of the organic solvent in Agent B is preferably 0 to 60% by mass, more preferably 0 to 50% by mass in the total amount of Agent B. Furthermore, the content rate of the organic solvent in the developable curable resin composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass in the total amount of the composition.

[0101] [Other Additive Components] In the developable curable resin composition, if necessary, further components such as a photoinitiator assistant, a cyanate compound, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, a chain transfer agent, a polymerization inhibitor, a copper corrosion inhibitor, an antioxidant, a rust inhibitor, fine powder silica, an organic bentonite, a thickener such as montmorillonite, an antifoaming agent and / or a leveling agent such as a silicone-based, fluorine-based, or polymer-based one, and a silane coupling agent such as an imidazole-based, thiazole-based, or triazole-based one, and a flame retardant such as a phosphorus compound such as a phosphinate, a phosphate ester derivative, or a phosphazene compound can be blended. These can be known substances in the field of electronic materials.

[0102] [Preparation Method] For the preparation of the above Agent A and Agent B, after weighing and blending each component, preliminary stirring is performed with a stirrer. Subsequently, it can be prepared by dispersing each component with a kneader and performing kneading.

[0103] Examples of the above kneader include a bead mill, a ball mill, a sand mill, a three-roll mill, a two-roll mill, etc. Among these, it is preferable to use a bead mill or a three-roll mill in terms of improving dispersibility.

[0104] [Uses] The developable curable resin composition is useful for forming a pattern layer as a permanent coating of a printed wiring board such as a solder resist, a coverlay, and an interlayer insulating layer, and is particularly useful for forming a solder resist. Further, since the developable curable resin composition can form a cured product having excellent film strength even in a thin film, it can also be suitably used for forming a pattern layer in a printed wiring board that requires thinning, such as a package substrate (a printed wiring board used in a semiconductor package). Furthermore, the cured product obtained from the developable curable resin composition can also be suitably used for a flexible printed wiring board.

[0105] The developable curable resin composition can be used not only for forming a pattern layer of a cured film but also for applications where no pattern layer is formed, such as a molding application (sealing application).

[0106] [Printed Wiring Board] A printed wiring board has a cured product obtained from a developable curable resin composition. As a method for manufacturing a printed wiring board, for example, a developable curable resin composition is adjusted to a viscosity suitable for a coating method using the above organic solvent, and then coated on a substrate by a method such as a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, or a curtain coating method. After that, the organic solvent contained in the composition is volatilized and dried (pre-dried) at a temperature of 60 to 100°C to form a tack-free resin layer.

[0107] Examples of the above substrate include a printed wiring board in which a circuit has been formed in advance with copper or the like, a flexible printed wiring board, a copper-clad laminate for a high-frequency circuit using materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven fabric epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluororesin / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate, etc. All grades (such as FR-4) of copper-clad laminates, as well as metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, etc. can be mentioned.

[0108] The evaporation drying carried out after applying the developable curable resin composition can be performed using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. (a method of countercurrent contacting the hot air in the dryer using a heat source of an air heating method by steam and a method of spraying onto a support from a nozzle).

[0109] After forming a resin layer on a substrate, it is selectively exposed to active energy rays through a photomask having a predetermined pattern, and the unexposed portion is developed with a dilute aqueous alkali solution (for example, a 0.3 to 3% by mass aqueous sodium carbonate solution) to form a pattern of a cured product.

[0110] Furthermore, by subjecting the cured product to heat curing (for example, 100 to 220 °C) after irradiation with active energy rays, or irradiating with active energy rays after heat curing, or performing final finishing curing (main curing) only by heat curing, a cured film excellent in various properties such as adhesion and hardness is formed.

[0111] As the exposure apparatus used for the above active energy ray irradiation, any apparatus equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc. and irradiating ultraviolet rays in the range of 350 to 450 nm may be used. Furthermore, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser based on CAD data from a computer) can also be used. The lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 450 nm. The exposure amount for image formation varies depending on the film thickness and the like, but generally it can be in the range of 10 to 1,000 mJ / cm 2 preferably 20 to 800 mJ / cm 2 within the range.

[0112] As the above-described development method, a dipping method, a shower method, a spray method, a brush method, etc. can be used, and as the developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. can be used.

[0113] <Thermal drying resin composition> Examples of the thermal drying resin composition include those containing a polyester resin, an inorganic filler, an organic solvent, etc., and it is used, for example, in an etching resist composition (hereinafter also referred to as a resist composition).

[0114] [Polyester resin] The above polyester resin is not particularly limited, and examples include polyesters obtained using a dicarboxylic acid component (dicarboxylic acid or its ester) and a glycol component as main starting materials. Examples of the dicarboxylic acid component include terephthalic acid, dimethyl terephthalate, 2,6-naphthalenedicarboxylic acid, isophthalic acid, phthalic acid, adipic acid, sebacic acid, and their esters. In particular, aromatic dicarboxylic acids such as terephthalic acid or dimethyl terephthalate or their esters are preferred. Examples of the glycol component include one or more of ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, neopentyl glycol, etc. In particular, ethylene glycol is preferred. When the polyester resin is a copolymerized polyester resin, examples of its dicarboxylic acid component include one or more of isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, sebacic acid, etc., and examples of its glycol component include one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, etc. As the polyester resin, for example, at least one structural unit selected from ethylene terephthalate, ethylene-2,6-naphthalate, propylene terephthalate, butylene terephthalate, hexamethylene terephthalate, cyclohexanedimethylene terephthalate, propylene-2,6-naphthalate, butylene-2,6-naphthalate, hexamethylene-2,6-naphthalate, cyclohexanedimethylene-2,6-naphthalate units, etc. is preferably used as the main constituent. Two or more polyesters may be mixed, or a copolymerized polyester may be used. The polyester resin may be crystalline or amorphous, but is preferably an amorphous polyester resin. Examples of commercially available products include Vyron 200, 630, GK-810 (amorphous polyester resin) manufactured by Toyobo Co., Ltd. The content rate of the polyester resin is not particularly limited, but it is preferably used at a ratio of 10 to 90% by mass, particularly 15 to 85% by mass, based on the total amount (including the solvent) of the heat-drying resin composition. Alternatively, the content rate of the polyester resin in the heat-drying resin composition is preferably 15 to 85% by mass, more preferably 20 to 80% by mass, in terms of solid content.

[0115] [Inorganic filler] Specific examples of the above inorganic filler include inorganic fillers such as barium sulfate, barium titanate, talc, clay, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride. Preferably, barium sulfate or talc is used alone or in combination of two or more. These inorganic fillers play a role in appropriately adjusting the viscosity during the preparation of the heat-drying resin composition, suppressing the curing shrinkage during heat drying, and improving the adhesion to the substrate. Among these, barium sulfate is particularly preferably used to improve the adhesion to the substrate.

[0116] The average primary particle size of the inorganic filler is preferably 15 μm or less, more preferably 10 μm or less. The average primary particle size (D50) can be measured by the laser diffraction / scattering method.

[0117] The content rate of the inorganic filler is not particularly limited, but it is preferably used at a rate of 8 to 100% by mass, particularly 20 to 60% by mass, based on the total amount of the heat-drying resin composition (including the solvent). If it is 8% by mass, particularly 20% by mass or more, the thixotropy of the composition is enhanced and the printing accuracy is good, and if it is 100% by mass or less, the leveling property is improved. Alternatively, the content rate of the inorganic filler in the heat-drying resin composition is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, in terms of solid content.

[0118] [Organic solvent] The heat-drying resin composition can contain an organic solvent other than the above three types of organic solvents for the purpose of preparing the composition and adjusting the viscosity when coating a substrate or a film within a range that does not impair the properties. As the organic solvent other than the above three types of organic solvents, for example, known and commonly used organic solvents such as petroleum ether, petroleum naphtha, and solvent naphtha can be used. These organic solvents may be used alone or in combination of two or more.

[0119] An antifoaming agent, a leveling agent, a coloring agent, a thickening agent, a silane coupling agent, etc. can be blended in the heat-drying resin composition as needed. Examples of the antifoaming agent that can be used include silicone-based antifoaming agents, fluorine-based antifoaming agents, and acrylic-based antifoaming agents. Examples of the silicone-based antifoaming agents include BYK (registered trademark)-063, -065, -066N, -081, -141, -323 manufactured by BYK Chemie Japan Co., Ltd., and KS-66, KS-69, X-50-1105G manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the fluorine-based antifoaming agents include MegaFac RS, F-554, F-557 manufactured by DIC Corporation, and examples of the acrylic-based antifoaming agents include Disparon OX-880EF, OX-70 manufactured by Kusumoto Chemical Co., Ltd.

[0120] In addition, as the coloring agent, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, As the thickener, known and commonly used thickeners including bentonite and finely divided silica are Examples of the silane coupling agent include halogen-containing silane coupling agents such as γ-chloropropylmethoxysilane, vinyl group-containing silane coupling agents such as vinyl ethoxysilane, vinyl methoxysilane, vinyl tris(β-methoxyethoxy)silane, vinyl triacetoxysilane, vinyl trichlorosilane, (meth)acryloyl group-containing silane coupling agents such as (meth)acryloxypropyltrimethoxysilane, glycidyl group-containing silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, mercapto group-containing silane coupling agents such as γ-mercaptopropyltrimethoxysilane, and amino group-containing silane coupling agents such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.

[0121] Among the above additives, in particular, by blending an antifoaming agent and / or a leveling agent, it is possible to prevent deterioration of surface smoothness and also prevent deterioration of interlayer insulation due to voids and pinholes. By blending a silane coupling agent, the adhesion to the substrate surface can be improved.

[0122] The viscosity of the heat-drying resin composition at 25°C is preferably in the range of 1 to 1,500 dPa·s, particularly preferably in the range of 10 to 1,000 dPa·s. When the viscosity of the heat-drying resin composition is 1 dPa·s or more, the heat-drying resin composition can form a coating film with a film thickness capable of well protecting the substrate as an etching resist by heat drying. On the other hand, when the viscosity of the heat-drying resin composition is 1,500 dPa·s or less, the composition is easy to handle, suitable for printing by screen printing, etc., and the resist stripping treatment after etching can be carried out simply and economically.

[0123] The heat-drying resin composition may contain a thermosetting material, for example, an epoxy compound, a curing agent, etc., if necessary.

[0124] In the method for manufacturing a substrate using a thermally drying resin composition, after adjusting the above-mentioned thermally drying resin composition into a uniform solution or dispersion, it is printed in a desired pattern with a film thickness of 5 to 100 μm, preferably 30 to 90 μm, more preferably 45 to 85 μm, on a substrate such as a glass substrate by screen printing or the like. Further, the patterned thermally drying resin composition can be dried by evaporating the organic solvent by heating in a drying furnace or the like at, for example, 50 to 200 °C, preferably 80 to 150 °C for 5 to 90 minutes, preferably 20 to 60 minutes, to form a dried coating film. The film thickness of the dried coating film is preferably in the range of 3 to 70 μm, particularly 30 to 60 μm.

[0125] The thermally drying resin composition is applicable not only to the screen printing method but also to printing methods such as the gravure method and the gravure offset method. Further, the thermally drying resin composition can be applied in multiple portions. As the application method in that case, wet-on-wet printing such as the conventionally known two-coat one-bake or dry-on-wet printing such as two-coat two-bake is possible.

[0126] Thereafter, when the thermally drying resin composition dried in a desired pattern is an etching resist resin composition, the coated substrate is subjected to an etching treatment with an etching solution. By the etching treatment, the substrate portion not covered with the resist is etched. Thereby, a glass molded product having a predetermined pattern can be obtained.

[0127] Examples of the etching solution include hydrofluoric acid alone or an etching solution containing hydrofluoric acid (for example, a mixture of hydrofluoric acid and a mineral acid (nitric acid, phosphoric acid, etc.), optionally containing one or more of weak acids such as acetic acid).

[0128] <Thermosetting resin composition> Examples of the thermosetting resin composition include those containing a carboxyl group-containing resin, an epoxy resin, a filler, an organic solvent, and the like.

[0129] [Carboxyl group-containing resin] The carboxyl group-containing resin contained in the thermosetting resin composition includes, for example, the carboxyl group-containing resin of the above <developable curable resin composition>. The content of the carboxyl group-containing resin in the thermosetting resin composition is preferably 15 to 85% by mass, more preferably 20 to 80% by mass, in terms of solid content.

[0130] [Epoxy resin] The epoxy resin contained in the thermosetting resin composition includes polyfunctional epoxy resins, for example, the polyfunctional epoxy compounds of the above <developable curable resin composition>. The content of the epoxy resin in the thermosetting resin composition is preferably 5 to 50% by mass, more preferably 1 to 45% by mass, in terms of solid content.

[0131] [Inorganic filler] In the thermosetting resin composition, an inorganic filler may be blended as necessary to increase the physical strength of the resulting cured product. As such an inorganic filler, for example, barium sulfate, spherical silica, or talc can be used. Further, metal oxides, metal hydroxides such as aluminum hydroxide, can also be used as inorganic fillers to obtain a white appearance and flame retardancy. The content of the inorganic filler in the thermosetting resin composition is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, in terms of solid content.

[0132] [Antioxidant] The thermosetting resin composition can contain antioxidants such as radical scavengers that inactivate generated radicals and peroxide decomposers that decompose generated peroxides into harmless substances to prevent the generation of new radicals in order to prevent oxidation. The antioxidant used in the present invention can prevent oxidative degradation of resins and the like and suppress yellowing. The antioxidant may be used alone or in combination of two or more.

[0133] [UV absorber] Generally, since polymer materials absorb light and thereby cause decomposition and / or deterioration, ultraviolet absorbers can be used in the resin composition in addition to antioxidants in order to take measures for stabilization against ultraviolet rays. Note that the ultraviolet absorber may be used alone or in combination of two or more kinds. By using the ultraviolet absorber and the antioxidant in combination, stabilization of the cured film obtained from the thermosetting resin composition can be achieved.

[0134] [Additive] In the thermosetting resin composition, if necessary, one or more known and commonly used additives such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and other coloring agents, organic fillers, hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, phenothiazine and other known and commonly used thermal polymerization inhibitors, fine powder silica, organic bentonite, montmorillonite and other known and commonly used thickeners, silicone-based, fluorine-based, polymer-based and other defoaming agents, leveling agents, imidazole-based, thiazole-based, triazole-based, silane coupling agent and other adhesion-imparting agents can be blended.

[0135] [Thermosetting catalyst] A thermosetting resin composition can contain a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. In addition to these, S-triazine derivatives such as guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct can also be used.

[0136] [Organic solvent] The thermosetting resin composition can contain an organic solvent other than the above three kinds of organic solvents for the purpose of preparing the composition and adjusting the viscosity when coating a substrate or film within a range that does not impair the properties. As the organic solvent other than the above three kinds of organic solvents, for example, known and commonly used organic solvents such as petroleum ether, petroleum naphtha, and solvent naphtha can be used. These organic solvents can be used alone or in combination of two or more.

[0137] The viscosity of the thermosetting resin composition at 25°C is preferably in the range of 0.1 to 2,000 dPa·s, more preferably in the range of 100 to 1,500 dPa·s, and even more preferably in the range of 300 dPa·s to 1,000 dPa·s.

[0138] When curing the thermosetting resin composition, the thermosetting resin composition may be set at about 100 to 250 °C, preferably about 100 to 200 °C. Further, in the case of photo-curing (dual cure), an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (super) high-pressure mercury lamp, an exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high-pressure mercury lamp can be used.

[0139] As the adherend of the thermosetting resin composition, all grades (such as FR-4) of copper-clad laminates using composite materials such as paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven fabric-epoxy resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc., polyimide film, PET film, glass substrate, ceramic substrate, wafer plate, etc. can be used.

[0140] The thermosetting resin composition is useful for forming a pattern layer as a permanent coating of a printed wiring board such as a solder resist, a coverlay, and an interlayer insulating layer. Also, depending on the composition, since it has excellent concealment and light-shielding properties, it can be suitably used for the decorative part of the touch panel part of electronic devices, etc., so a glass plate is suitable as the adherend. In this case, as the glass substrate, glass having a good transparency equivalent to that of a general float glass or a glass for a substrate of a flat display device such as a liquid crystal panel can be used. However, particularly considering the contact use as a touch panel, it is desirable to use tempered glass having a high surface compressive stress. Tempered glass is formed with a compressive stress layer on the surface by an ion exchange method, an air-cooled strengthening method, etc. However, if an asymmetric cross-section in the thickness direction is created by processing from one side with a diamond cutter, a laser cutter, etc., cracks are likely to occur. Therefore, it is desirable to make further improvements in the process of dividing the cover glass described later.

[0141] When applying the thermosetting resin composition to an adherend, for example, adjust the viscosity to a value suitable for the coating method with an organic solvent, and apply it onto the substrate by methods such as dip coating method, flow coating method, roll coating method, bar coater method, screen printing method, curtain coating method, etc. Then, volatilize and dry (pre-dry) the organic solvent contained in the composition at a temperature of about 60 to 100 °C.

Examples

[0142] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, "parts" and "[%]" are all based on mass unless otherwise specified.

[0143] [Synthesis Example 1] (Preparation of Resin 1) 220 parts of a cresol novolak type epoxy resin (EPICRON N-695, manufactured by DIC Corporation, epoxy equivalent: 209 g / eq to 219 g / eq) were placed in a four-necked flask equipped with a stirrer and a reflux condenser, 214 parts of carbitol acetate were added, and the mixture was heated and dissolved. Next, 0.46 part of hydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 °C, 72 parts of acrylic acid were gradually added dropwise, and the reaction was carried out for 16 hours. The reaction product was cooled to 80 to 90 °C, 91.2 parts of tetrahydrophthalic anhydride were added, and the reaction was carried out for 8 hours. After cooling, it was taken out. The carboxyl group-containing photosensitive resin solution thus obtained had a non-volatile content of 65% and an acid value of the solid content of 85 mgKOH / g. This is described as Resin 1 (see Synthesis Example 2 of JP-A-2002-296776).

[0144] [Examples 1 to 12, Comparative Examples 1 to 4] In the case of a two-component resin composition in which Agent A and Agent B described in Table 1 are mixed and used, Agent A and Agent B were each prepared by mixing the materials in the compositions described in Table 1, stirring with a dissolver, and further kneading with a three-roll mill. Then, Agent A and Agent B were mixed with a dissolver in the combinations described in Table 2 to obtain a resin composition containing an organic solvent (Examples 1 to 3, 5, and 8 to 12, Comparative Examples 1 to 4). On the other hand, in the case of the one - component resin composition composed of Agent A described in Table 1, Agent A described in Table 2 was stirred with a dissolver and further kneaded with a three - roll mill to prepare a resin composition containing the organic solvent described in Table 2 (Examples 4, 6, and 7). The obtained resin composition containing the organic solvent was filled into a cylindrical container made of high - density polyethylene (HDPE) with an internal volume of 1 L at the volume filling ratio described in Table 2 (the thickness of the container material is described in Table 2). Then, the stirrability, loss amount, label peeling of the container, and handleability of each resin composition were evaluated. The results are shown in Table 2.

[0145] Viscosity For all of Agent A, Agent B, and the resin composition, in accordance with JIS - Z8803:2011, specifically, the 30 - second value measured under the conditions of 25 °C and a rotor rotation speed of 5.0 rpm using a cone - plate type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., TVE - 33H, rotor 3°×R9.7) in accordance with Method 10 "Viscosity Measurement Method by Cone - Plate Rotational Viscometer" of JIS - Z8803:2011 was measured.

[0146] (1) Evaluation of stirrability Using a stirrer, the resin composition containing the organic solvent in the container was stirred under the conditions of a rotating blade diameter of 50 mm, a rotation speed of 800 rpm, a temperature of 22 °C, and for 5 minutes. The workability during stirring was evaluated according to the following criteria. <Evaluation criteria> 3: The resin composition can be stirred without problems. 2: The resin composition is slightly difficult to stir, but stirring itself is possible. 1: The resin composition is very difficult to stir and hardly stirred at all.

[0147] (2) Evaluation of loss amount Using a stirrer, the resin composition containing the organic solvent in the container was stirred under the conditions of a rotating blade diameter of 50 mm, a rotation speed of 800 rpm, a temperature of 22 °C, and for 5 minutes. After stirring, the loss amount of the resin composition was evaluated according to the following criteria. <Evaluation criteria> 3: There is no loss of the resin composition. There is no overflow of the resin composition from the container, no residue inside the container of the resin composition, or no adhesion to the stirring blade. 2: There is a slight loss of the resin composition. There is a slight overflow of the resin composition from the container, or a slight residue inside the container of the resin composition or adhesion to the stirring blade. 1: There is a significant loss of the resin composition. There is a significant overflow of the resin composition from the container, or a significant residue inside the container of the resin composition or adhesion to the stirring blade.

[0148] (3) Evaluation of label peeling of the container The inner stopper (made of polypropylene (PP)) and the cap (made of high-density polyethylene (HDPE)) corresponding to the container filled with each resin composition were used to seal it. Subsequently, a 3M Post-it (registered trademark) (ordinary adhesion 75mm X 75mm) was pasted on the side surface of the container. Then, the container sealed with the Post-it pasted was stored in a constant temperature bath at a temperature of 50°C and a humidity of 40% for 24 hours, and the peeling state of the Post-it was evaluated. <Evaluation criteria> 3: The Post-it has not peeled off at all from the side surface of the container. 2: The Post-it has peeled off slightly from the side surface of the container, but has not peeled off completely. 1: The Post-it has peeled off completely from the side surface of the container and fallen to the ground.

[0149] (4) Evaluation of handleability Using a stirrer, the resin composition containing an organic solvent in the container was stirred under the conditions of a rotation blade diameter of 50 mm, a rotation speed of 800 rpm, a temperature of 22°C, and for 5 minutes. The handleability of the container immediately after stirring was evaluated. <Evaluation criteria> 3: The container can be handled without any particular problem. 2: There is a slight deformation of the container, but there is no problem in handling it. 1: The container is heavy and may cause an obstacle to transportation.

Table 1

Table 2

[0150] · Resin 1: Photosensitive resin solution containing carboxyl groups (Synthesis Example 1), the values in the table are the values of the solid content · Resin 2: BYRON 200, manufactured by Toyobo Co., Ltd., amorphous polyester resin, Mn 17,000 · Photopolymerizable monomer 3: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate · Photopolymerizable monomer 4: NK Ester A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate · Photoinitiator 5: IRGACURE OXE02, manufactured by BASF Japan Ltd., oxime ester-based photo radical polymerization initiator · Photoinitiator 6: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phosphine oxide-based photo radical polymerization initiator · Inorganic filler 7: BARIACE B-30, manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate, average particle size (D50) 0.3 um · Inorganic filler 8: Cristalite 5K, manufactured by Tatsumori Co., Ltd., crystalline silica, average particle size (D50) 1 um · Epoxy resin 9: EPICRON 850, manufactured by DIC Corporation, bisphenol A type epoxy resin, epoxy equivalent 183 - 193 g / eq. · Epoxy resin 10: EPICRON N-660, manufactured by DIC Corporation, cresol novolak type epoxy resin, epoxy equivalent 202 - 212 g / eq. · Organic solvent 11: Ethyl acetate dukisol, ester-based hydrocarbon having a glycol skeleton, manufactured by Shinko Organic Chemical Industry Co., Ltd., diethylene glycol monoethyl ether acetate, boiling point 217 °C · Organic solvent 12: Dowanol DPM, alcohol-based hydrocarbon having a glycol skeleton, manufactured by Dow Chemical Japan Ltd., dipropylene glycol monomethyl ether, boiling point 188 °C · Organic solvent 13: Progarde DMM, an ether-based hydrocarbon having a glycol skeleton, manufactured by Dow Chemical Japan Ltd., dipropylene glycol dimethyl ether, boiling point 177°C · Organic solvent 14: Ipzol 100, an aromatic hydrocarbon, manufactured by Idemitsu Kosan Co., Ltd., boiling point 160°C to 170°C · Organic solvent 15: Solvent #150, an aromatic hydrocarbon, manufactured by Sankyo Chemical Co., Ltd., boiling point 190°C to 230°C

[0151] The containers containing the resin compositions of Examples 1 to 12 are all good in terms of the evaluation of the stirrability, loss amount, and label peeling of the resin compositions. Among them, Examples 1 to 7, 11, and 12 are all evaluated as "3" and are particularly excellent.

[0152] On the other hand, the containers containing the resin compositions of Comparative Examples 1 and 2 had label peeling because aromatic hydrocarbons were used as the organic solvent. Also, the containers containing the resin compositions of Comparative Examples 3 and 4 had unfavorable results in terms of stirrability and loss amount because the filling ratio of the resin compositions into the containers was outside the desired range.

Industrial Applicability

[0153] The plastic container for housing the resin composition of the present invention has good stirrability of the resin composition inside the plastic container. Also, deterioration of the plastic container (especially polyolefin container) and peeling of the label on the container surface are less likely to occur. Therefore, it is preferably used as a plastic container for housing resin compositions such as solder resist for printed wiring boards, etching resist for glass substrates, and resin for forming decorative parts of touch panels.

Claims

1. A plastic container containing a resin composition, wherein the volume ratio of the resin composition is 30 vol% or more and 80 vol% or less with respect to the volume of the plastic container, and the resin composition contains at least one organic solvent selected from the group consisting of ester-based hydrocarbons having a glycol skeleton, alcohol-based hydrocarbons having a glycol skeleton, and ether-based hydrocarbons having a glycol skeleton. A plastic container containing a resin composition.

2. The plastic container according to claim 1, wherein the material of the plastic container is a polyolefin resin.

3. The ester-based hydrocarbon having a glycol skeleton is an ester of a polyalkylene glycol monoalkyl ether and a carboxylic acid compound, the alcohol-based hydrocarbon having a glycol skeleton is a polyalkylene glycol monoalkyl ether, and the ether-based hydrocarbon having a glycol skeleton is a polyalkylene glycol dialkyl ether. A plastic container containing the resin composition according to claim 1.

4. The plastic container according to claim 1, wherein the thickness of the plastic of the plastic container is 1 mm or more and 5 mm or less.

5. The plastic container according to claim 1, wherein the shape of the plastic container is cylindrical.

6. The plastic container according to claim 1, wherein the volume of the plastic container is 0.1 L or more and 20 L or less.

7. The plastic container according to claim 1, wherein the viscosity of the resin composition at 5 rpm at 25 °C is 0.1 dPa·s or more and 2,000 dPa·s or less.

8. The plastic container according to claim 1, wherein the resin composition is a developable curable resin composition, a heat-drying type resin composition, or a thermosetting resin composition.

9. The plastic container according to claim 8, wherein the resin composition is a developable curable resin composition.

10. The plastic container according to claim 8, wherein the resin composition is a heat-drying type resin composition.

11. The plastic container according to claim 8, wherein the resin composition is a thermosetting resin composition.

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