Alkali-soluble ultraviolet-curable silicon-containing linear polymer, ultraviolet-curable composition comprising same, and use thereof

Abstract

Provided are: an ultraviolet-curable linear polymer which has high ultraviolet-curable properties and good alkali solubility even without using a polyfunctional polymerizable monomer, and which has excellent ultraviolet-curable properties; and an ultraviolet-curable composition containing the ultraviolet-curable linear polymer. And the cured product (cured film) thereof has sufficient mechanical strength and good transparency. An ultraviolet-curable linear polymer having two (meth) acrylate groups, two carboxyl groups, and at least two silicon atoms in a repeating unit, and having solubility in an alkaline aqueous solution as a whole, and an ultraviolet-curable composition comprising the same.

Description

Technical Field

[0001] The present invention relates to an alkali-soluble ultraviolet-curable silicon-containing linear polymer that can be cured by actinic rays, such as ultraviolet rays or electron beams, and an ultraviolet-curable composition containing the same. The silicon-containing linear polymer of the present invention has high solubility in alkaline aqueous solutions and good ultraviolet curability without using a multifunctional polymerizable monomer, and therefore exhibits excellent photolithographic performance, and is suitable for use as an insulating material for electronic devices and electrical equipment that require patterning, and is particularly suitable as a material for a coating agent. Background Art

[0002] Silicone resins have been used as coating agents, potting agents, and insulating materials for electronic devices and electrical equipment due to their high heat resistance and excellent chemical stability. Among silicone resins, ultraviolet curable silicone compositions have also been reported.

[0003] Touch panels are used in various display devices such as mobile devices, industrial equipment, and car navigation. In order to improve its sensing sensitivity, it is necessary to suppress the film response from the light-emitting parts such as light-emitting diodes (LEDs) and organic EL devices (OLEDs), and an insulating layer is usually arranged between the light-emitting part and the touch screen. On the other hand, thin display devices such as OLEDs have a structure in which multiple functional thin layers are stacked. In recent years, the following research has been conducted: by stacking an insulating layer formed by a high-refractive-index acrylate polymer and a multifunctional polymerizable monomer on the touch screen layer to improve the visibility of the display device. (For example, Patent Documents 1 and 2)

[0004] On the other hand, Patent Document 3 discloses a photolithographic curable composition composed of a silsesquioxane having a carboxyl group and a methacryloxy group, a multifunctional polymerizable monomer, an inorganic filler, a polymerization initiator, and an organic solvent. In this composition, in order to improve the sensitivity during curing and the adhesion of the cured product, the multifunctional polymerizable monomer is contained at a concentration of 33% or more of the total curable component. Therefore, it is difficult to increase the content of silicone in the obtained cured product to a certain level, and sometimes the heat resistance and other properties required of the silicone material are impaired.

[0005] In addition, patent document 4 discloses a straight-chain alkali-soluble resin having a carboxyl group and a (meth) acrylate group in a repeating unit and a biphenyl skeleton as the main body, and a patternable curable composition containing the same. However, the rigidity of the cured product obtained by the present composition is high, so there is room for improvement in the mechanical strength (especially brittleness) of the coating with a large film thickness. That is, although an alkali-soluble and silicon-containing ultraviolet curable composition is disclosed, there is no record or suggestion of an alkali-soluble ultraviolet curable silicon-containing straight-chain polymer and an ultraviolet curable composition containing the same, which has high solubility in alkaline aqueous solution and shows high ultraviolet curability even without the deployment of a multifunctional polymerizable monomer, and provides a transparent cured product.

[0006] On the other hand, in non-patent document 5 (particularly FIG. 4 ), a co-diol type non-carbon binder polymer containing a disiloxane bond, a carboxyl group on an aromatic ring containing a fluoromethyl group, and a (meth)acrylate group in a repeating unit is proposed as a photolithographic material. However, there is no evaluation of the alkali solubility of the polymer, and there is no description or suggestion of a silicon-containing alkali-soluble ultraviolet curable linear polymer that provides a transparent cured product even without using a multifunctional polymerizable monomer, and particularly an ultraviolet curable composition with excellent ultraviolet curability.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2013-140229

[0010] Patent Document 2: Japanese Patent Application Publication No. 2021-61056

[0011] Patent Document 3: Japanese Patent Application Publication No. 2018-123234

[0012] Patent Document 4: Japanese Patent Application Publication No. 2008-9401

[0013] Non-patent literature

[0014] Non-patent document 1: Materials Sciences and Applications, 2019, 10, pp. 687-696 Summary of the invention

[0015] Problems to be solved by the invention

[0016] As described above, there is still a need for a UV-curable linear polymer and a UV-curable composition containing the same, wherein the UV-curable linear polymer has a high content of silicon components in the obtained cured product even without using a multifunctional polymerizable monomer, has high UV curability and good alkali solubility, and the cured product (cured film) has sufficient mechanical strength and good transparency.

[0017] Solutions for solving problems

[0018] The present invention has been made to solve the above-mentioned problems. The present invention has been made by discovering that a UV-curable silicon-containing linear polymer and a UV-curable composition containing the same have excellent coating properties and alkali solubility on a substrate, and that even without using a multifunctional polymerizable monomer, the cured product (cured film) has sufficient mechanical strength and good transparency. The UV-curable silicon-containing linear polymer has two (meth)acrylate groups, two carboxyl groups and at least two silicon atoms in a repeating unit, and the polymer as a whole is soluble in an alkaline aqueous solution.

[0019] That is, the present invention relates to an ultraviolet-curable silicon-containing linear polymer and an ultraviolet-curable composition containing the same. The composition is cured by forming a bond based on an ultraviolet-curable functional group, but its curing method is not limited to ultraviolet irradiation, and any method that can cause a curing reaction by the ultraviolet-curable functional group can be used. For example, high-energy rays other than ultraviolet rays such as electron beam irradiation can be used to cure the composition of the present invention.

[0020] The ultraviolet curable silicon-containing linear polymer is preferably a substance represented by the following structural formula (1).

[0021] [Chemical formula 1]

[0022]

[0023] (Where R 1 is an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 2 is a divalent linking group selected from an oxygen atom (—O—), a divalent hydrocarbon group having 1 to 10 carbon atoms, or a silicon-containing group represented by the following formula (2), R 3 Each of them has one (meth)acrylate group, the carbon number of the part other than the (meth)acrylate group is 5 to 10 and may contain a divalent linking group of heteroatoms, A is a divalent linking group having two carboxyl groups, X is a hydroxyl group or a group represented by the following formula (3), Y is a hydrogen atom or a group represented by the following formula (4), and the number of repeating units n is a number in the range of 1 to 100.

[0024] [Chemical formula 2]

[0025]

[0026] (Where R 1 is the above-mentioned group, and p is a number from 1 to 20. )

[0027] [Chemical formula 3]

[0028]

[0029] (Where R 1 ~R 3 is the above-mentioned group, and * is the bonding site with the carbonyl group. )

[0030] [Chemical formula 4]

[0031]

[0032] (In the formula, A is the above-mentioned group, and * is the bonding site with the oxygen atom.)

[0033] More preferably, the above R 3 It can be represented by the following structural formula 5a ~ 5d More than one divalent linking group is shown.

[0034] [Chemical formula 5]

[0035]

[0036] (Where R 4 is a hydrogen atom or a methyl group, * is a site bonded to a silicon atom, and ** is a site bonded to an oxygen atom.)

[0037] More preferably, the above R 2 It may be a divalent linking group selected from an oxygen atom (—O—) and a silicon-containing group represented by the above formula (2).

[0038] More preferably, the X may be a group represented by the above formula (3), and the Y may be a hydrogen atom.

[0039] More preferably, the above n may be a number in the range of 2-20.

[0040] More preferably, the above-mentioned A may be a divalent linking group not including an aromatic group.

[0041] The solubility of the ultraviolet curable silicon-containing straight-chain polymer of the present invention in alkaline aqueous solution is preferably such that when the straight-chain polymer is applied on a glass plate in a thickness of 4 μm after coating, the coating film is then immersed in a 2.38 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute and then washed with water, the mass reduction rate of the coating film composed of the organopolysiloxane is 90 mass % or more, more preferably 95 mass % or more or 98 mass % or more.

[0042] The method for producing the ultraviolet curable silicon-containing linear polymer according to the present invention may be a method comprising the step of reacting an organosilicon compound represented by the following formula (6) with a tetracarboxylic acid represented by the following formula (7a) or a tetracarboxylic dianhydride represented by the following formula (7b).

[0043] [Chemical formula 6]

[0044]

[0045] (Where R 1 ~R 3 is the group mentioned above.)

[0046] [Chemical formula 7]

[0047]

[0048] [Chemical formula 8]

[0049]

[0050] (Wherein, Z is a tetracarboxylic acid residue.)

[0051] The present invention further provides an ultraviolet curable composition comprising at least:

[0052] (A) the above-mentioned ultraviolet curable silicon-containing linear polymer; and

[0053] (B) a photopolymerization initiator in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the component (A);

[0054] Also optionally contains:

[0055] (C) an organic solvent;

[0056] (D) An ultraviolet curable branched polysiloxane in an amount of 0 to 1,000 parts by mass based on 100 parts by mass of the component (A).

[0057] The present invention further provides an insulating coating agent comprising the ultraviolet curable composition.

[0058] The present invention further provides a cured product of the ultraviolet curable composition and a method of using the cured product as an insulating coating.

[0059] The present invention further provides a display device including a layer composed of a cured product of the ultraviolet curable composition, such as a liquid crystal display, an organic EL display, and an organic EL flexible display.

[0060] Effects of the Invention

[0061] The ultraviolet curable silicon-containing linear polymer of the present invention shows high ultraviolet curability even without the deployment of multifunctional polymerizable monomers, and can be designed to have a high content of silicon-containing components in the obtained cured product, and has good coating properties on the substrate. In the development process performed to form a pattern of a desired shape, it shows high solubility in the commonly used alkaline aqueous solution, so in the development process accompanied by selective ultraviolet irradiation, the unreacted / uncured linear polymer and the curable composition containing it can be easily removed by a washing operation using an alkaline aqueous solution, so that high-precision patterning can be achieved through a simple process. In addition, the cured product formed by the ultraviolet curable composition containing the ultraviolet curable linear polymer of the present invention has the advantages of being optically transparent and being able to design hardness in a wide range. Therefore, the curable composition involved in the present invention is useful as a material for an insulating layer, especially a patterning material and a coating material. DETAILED DESCRIPTION

[0062] Hereinafter, the configuration of the present invention will be described in further detail.

[0063] The ultraviolet curable silicon-containing linear polymer of the present invention has two (meth)acrylate groups, two carboxyl groups and at least one siloxane bond in a repeating unit, and the polymer as a whole is soluble in an alkaline aqueous solution (sometimes expressed as "alkali-soluble" in the present invention). In addition, the ultraviolet curable composition of the present invention contains (A) the above-mentioned ultraviolet curable silicon-containing linear polymer and (B) a photopolymerization initiator as essential components, and may also optionally contain (C) an organic solvent and (D) an ultraviolet curable branched polysiloxane.

[0064] In this specification, "(meth)acrylate group" refers to a group selected from methacrylate group and acrylate group, and may include both. In addition, the compound having a (meth)acrylate group includes both methacrylate compounds and acrylate compounds. It should be noted that "a structure having a (meth)acrylate group on a carbon atom" refers to a structure having a (meth)acrylate group on a carbon atom in the connecting group R 3 The carbon atom has a -OC(=O)-C(R 4 )=CH 2(R in the formula 4 The structure of a group containing a (meth)acrylate group represented by (a) is a hydrogen atom or a methyl group.

[0065] Here, alkali solubility means that the formed coating film is soluble in a commonly used alkaline aqueous solution in the development process for forming a pattern of a desired shape. As the alkaline aqueous solution, well-known alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, and quaternary ammonium salts are provided, but an aqueous solution of tetramethylammonium hydroxide is generally used, and in the present invention, it means that the coating film is soluble in the alkaline aqueous solution.

[0066] More specifically, "soluble in alkaline aqueous solution" means that when the ultraviolet curable silicon-containing linear polymer involved in the present invention is coated on a glass plate in a thickness of 4 μm, and then the coating film is immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute and then washed with water, the mass reduction rate of the coating film composed of the linear polymer is 90% by mass or more, and in particular, when the mass reduction rate of the coating film is 95% by mass or more or 98% by mass or more when evaluated by the above method, the solubility in alkaline aqueous solution is particularly excellent. It should be noted that the method of coating the linear polymer on the glass plate is usually spin coating, etc., and when the organic solvent described later is used for coating, it is necessary to remove the organic solvent in advance by drying, etc. Further, if the composition is mainly composed of the ultraviolet curable silicon-containing linear polymer of the present invention, the solubility of the ultraviolet curable composition containing the linear polymer involved in the present invention in alkaline aqueous solution can be evaluated by the above method. The water washing step is generally performed by immersion in a water bath at room temperature (25° C.) or by running water at a flow rate similar to that of household tap water for about 10 to 15 seconds to avoid adverse effects on the formed pattern and substrate.

[0067] It should be noted that the ultraviolet curable silicon-containing straight-chain polymer involved in the present invention has a tendency to further improve the solubility in alkaline aqueous solutions compared with organic polysiloxanes having branched / resinous molecular structures such as silsesquioxane units. Among these straight-chain polymers, when the solubility of a coating film composed of the straight-chain polymer in an alkaline aqueous solution is evaluated by the above-mentioned method, there is a tendency that a straight-chain polymer with particularly excellent alkali solubility can be obtained with a mass reduction rate of 98% by mass or more of the coating film.

[0068] [UV-curable silicon-containing linear polymer]

[0069] The ultraviolet curable silicon-containing linear polymer of the present invention is a linear polymer having two (meth)acrylate groups as ultraviolet curable groups, two carboxyl groups as hydrophilic groups, and at least two silicon atoms in a repeating unit, and having the above-mentioned alkali solubility. In particular, the ultraviolet curable silicon-containing linear polymer of the present invention must have the above-mentioned alkali solubility as a whole polymer, and a polymer having two (meth)acrylate groups as ultraviolet curable groups, two carboxyl groups, and at least two silicon atoms in a repeating unit but not having sufficient alkali solubility is not included in the scope of the present invention.

[0070] Specifically, the ultraviolet curable silicon-containing linear polymer of the present invention is preferably represented by the following structural formula (1) from the viewpoint of its alkali solubility.

[0071] [Chemical formula 9]

[0072]

[0073] (Where R 1 is an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 2 is a divalent linking group selected from an oxygen atom (—O—), a divalent hydrocarbon group having 1 to 10 carbon atoms, or a silicon-containing group represented by the following formula (2), R 3 Each of them has one (meth)acrylate group, the carbon number of the part other than the (meth)acrylate group is 5 to 10, and the divalent linking group may contain a heteroatom, A is a divalent linking group having two carboxyl groups, X is a hydroxyl group or a group represented by the following formula (3), Y is a hydrogen atom or a group represented by the following formula (4), and n is a number in the range of 1 to 100.

[0074] [Chemical formula 10]

[0075]

[0076] (Where R 1 is the above-mentioned group, and p is a number from 1 to 20. )

[0077] [Chemical formula 11]

[0078]

[0079] (Where R 1 ~R 3 is the above-mentioned group, and * is the bonding site with the carbonyl group. )

[0080] [Chemical formula 12]

[0081]

[0082] (In the formula, A is the above-mentioned group, and * is the bonding site with the oxygen atom.)

[0083] Here, R 1 It is a monovalent hydrocarbon group having 1 to 10 carbon atoms and being unsubstituted or substituted by fluorine. The monovalent hydrocarbon group having 1 to 10 carbon atoms and being unsubstituted or substituted by fluorine is preferably a group selected from an alkyl group having 1 to 10 carbon atoms and being unsubstituted or substituted by fluorine, a cycloalkyl group, an arylalkyl group and an aryl group. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, pentyl, hexyl, octyl and the like, but methyl and hexyl are particularly preferred. Examples of the cycloalkyl group include cyclopentyl and cyclohexyl. Examples of the arylalkyl group include benzyl and phenethyl. Examples of the aryl group include phenyl and naphthyl. Examples of the monovalent hydrocarbon group having fluorine as an example include 3,3,3-trifluoropropyl and 3,3,4,4,5,5,6,6,6-nonafluorohexyl, but 3,3,3-trifluoropropyl is preferred.

[0084] In addition, R 2 It is a divalent linking group selected from an oxygen atom (—O—), a divalent hydrocarbon group having 1 to 10 carbon atoms, or a silicon-containing group represented by the following formula (2).

[0085] (OSiR 1 2 ) p O (2)

[0087] (Where R 1 is the above-mentioned group, and p is a number from 1 to 20. )

[0088] As R 2 The divalent hydrocarbon group having 1 to 10 carbon atoms is a group selected from linear, branched, cyclic or branched alkylene groups including a ring, arylene groups and arylene alkylene groups, and refers to silylene groups, silylene groups and silylene arylene alkylene groups formed between two silicon atoms in the repeating unit in the structural formula (1). Examples of the alkylene group include methylene, ethylene, propylene, butylene, hexylene, dimethylmethylene, 1,4-cyclohexyl, 1,4-cyclohexane dimethylene and the like, but methylene, ethylene and hexylene groups are preferably used. Examples of the arylene group include 1,3-phenylene and 1,4-phenylene groups, but 1,4-phenylene groups are preferably used. Examples of the arylene alkylene group include 1,4-phenylenedimethylene and 1,4-phenylenediethylene. By appropriately selecting the group, physical properties such as hardness and softening point of the produced linear polymer can be controlled. By using a linear alkylene group or arylene group having a small number of carbon atoms, a polymer having a high softening point can be designed.

[0089] As R2 The oxygen atom (—O—) is an oxygen atom constituting the disiloxane bond in the repeating unit of the above structural formula (1).

[0090] As R 2 The silicon-containing group represented by formula (2) is a siloxane bond formed between two silicon atoms in the repeating unit of formula (1), and the (p+2) silicon atoms are the number of siloxane units contained in the repeating unit, that is, the number of silicon atoms.

[0091] R in formula (2) 1 is an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include the same groups as those mentioned above. 2 The number of siloxane units in is 1 to 20. By adjusting this value, the same effects as above can be achieved. That is, the physical properties such as hardness and softening point of the produced linear polymer can be controlled.

[0092] From the viewpoint of the ease of controlling the above-mentioned physical properties and the production cost, the divalent linking group R between silicon atoms 2 It is preferably a group selected from an oxygen atom (-O-) and a silicon-containing group represented by the above formula (2). In particular, R 2 Particularly preferred are oxygen atoms or silicon-containing groups represented by formula (2) in which p is in the range of 1 to 10 or 1 to 3. By including a disiloxane bond or a polysiloxane bond consisting of (p+2) siloxane units in the repeating units constituting the ultraviolet curable silicon-containing linear polymer represented by formula (1), it is possible to design a cured product, i.e., a coating, having both hardness and toughness using the polymer.

[0093] R 3 Each of them has one (meth)acrylate group, and the number of carbon atoms in the part other than the (meth)acrylate group is 5 to 10, and they may contain heteroatoms such as oxygen atoms. 3 As long as there is one (meth)acrylate group, the structure of the entire connecting group is not limited.

[0094] In a preferred embodiment, R 3 It may be a group selected from a linear, branched, cyclic or branched alkylene group including a cyclic group, an arylene group and an arylenealkylene group having 5 to 10 carbon atoms, and is a group having a (meth)acrylate group bonded to a carbon atom thereof. In addition, heteroatoms such as oxygen atoms may be contained at any position of these linking groups, and in this case, it is more preferable to contain one oxygen atom.

[0095] R is particularly preferred 3A group having a (meth)acrylate group bonded to a carbon atom of a linear, branched or cyclic (including partially cyclic) alkylene group having 6 to 8 carbon atoms and which may contain an oxygen atom between carbon atoms; a group having a -OC(=O)-C(R 4 )=CH 2 (R in the formula 4 It should be noted that from the viewpoint of requiring higher ultraviolet curability, R 4 is a hydrogen atom, i.e. R 3 It is preferred to have an acrylate group bonded to a carbon atom on the alkylene group.

[0096] In a particularly preferred embodiment, R 3 According to the following structural formula 5a ~ 5d More than one divalent linking group is shown.

[0097] [Chemical formula 13]

[0098]

[0099] (Where R 4 is a hydrogen atom or a methyl group, * is a site bonded to a silicon atom, and ** is a site bonded to an oxygen atom.)

[0100] Furthermore, A in the main chain skeleton is a divalent linking group substituted by two carboxyl groups. As long as there are two carboxyl groups, the structure of the entire linking group is not limited. In a preferred embodiment, the divalent linking group is a group having a structure in which two hydrogen atoms of a group selected from a linear, branched, cyclic or branched alkylene group including a ring, an arylene group and an arylene alkylene group are substituted by a carboxyl group (-COOH). In addition, halogen atoms, heteroatoms or groups containing heteroatoms may be contained at any part of these linking groups. As halogen atoms, fluorine atoms, chlorine atoms and bromine atoms can be exemplified. As specific examples of heteroatoms or groups containing heteroatoms, the following formula (8) can be cited: 8a ~ 8f , but are not limited to these.

[0101] [Chemical formula 14]

[0102]

[0103] Specific examples of the divalent linking group obtained by removing two carboxyl groups from the above A include: phenylene, butylene, bromine-substituted phenylene, cyclohexylene, cyclopentylene, cyclobutylene, benzophenylene, naphthylene, bromine-substituted naphthylene, bicyclohexylene, perylene, bromine-substituted perylene, 5,5'-(9H-fluorene-9,9-diyl)biphenylene, bicyclo[2,2,2]oct-7-enyl, bicyclo[2,2,2]octyl, biphenylene, N,N,N',N'-tetramethyleneethylene, ethylene glycol dibenzoyl, and the like.

[0104] As the above-mentioned A, it is preferred that two of the hydrogen atoms on the carbon atom are replaced by a carboxyl group (-COOH), and an alkylene, arylene and arylene alkylene group optionally have an oxygen atom (above 8a) or a carbonyl group (above 8c) between its carbon-carbon bonds, and it is particularly preferred that two of the hydrogen atoms on the carbon atoms on the divalent connecting group selected from phenylene, butylene, cyclohexylene and benzophenylene are replaced by a carboxyl group (-COOH). It should be noted that, from the viewpoint of ultraviolet curability, as A, it is most preferred that two of the hydrogen atoms on the carbon atoms on the alkylene group that do not contain an aromatic group are replaced by a carboxyl group (-COOH), and specifically, two of the hydrogen atoms on the carbon atoms on the butylene or cyclohexylene group are replaced by a carboxyl group (-COOH). It should be noted that, in the case where the divalent connecting group A has an aromatic group, by using the (D) ultraviolet curable branched polysiloxane described later in the ultraviolet curable composition, sufficient ultraviolet curability can be achieved in practice.

[0105] By appropriately selecting the chemical structure of the divalent linking group A, the physical properties, in particular the softening point, of the linear polymer of the present invention can be controlled. For example, by introducing a divalent linking group A from an aromatic tetracarboxylic acid residue, the softening point of the polymer as a whole tends to be higher. On the other hand, in the case of introducing a divalent linking group A from a linear tetracarboxylic acid residue, since A does not contain an aromatic group, the softening point of the polymer as a whole tends to be lower. For example, in the case of wishing to suppress the surface viscosity of the cured layer formed by curing the linear polymer of the present invention, by using a polymer containing a divalent linking group A having an aromatic group (= having a tendency to have a high softening point, but sometimes having low UV curability), and by using (D) a UV curable branched polysiloxane in the UV curable composition, sufficient UV curability can be achieved in practice, and a composition design that suppresses the surface viscosity of the cured layer can be achieved.

[0106] On the other hand, in the silicon-containing linear polymer of the present invention, the number of repeating units having two (meth)acrylate groups as ultraviolet curable groups, two carboxyl groups as hydrophilic groups, and at least two silicon atoms (i.e., the degree of polymerization consisting of the repeating units) is not particularly limited as long as it is 1 or more, but from the viewpoint of setting the softening point of the polymer within a practically appropriate range, it is preferably in the range of 1 to 100. When the number of the repeating units increases, the softening point of the silicon-containing linear polymer of the present invention tends to increase. It should be noted that the silicon-containing linear polymer of the present invention has high alkali solubility regardless of the number of its repeating units.

[0107] In the silicon-containing linear polymer of the present invention represented by the above structural formula (1), n ​​is preferably a number in the range of 1-100, more preferably a number in the range of 2-20, or 2-15.

[0108] It should be noted that, in the silicon-containing linear polymer of the present invention, the molecular weight of the entire polymer is not particularly limited, but from the viewpoint of the coating properties as a patterning material or a coating material and the mechanical strength of the coated film, the weight average molecular weight converted to polystyrene by gel permeation chromatography is preferably in the range of 1,000 to 100,000, and more preferably in the range of 1,000 to 20,000. In the silicon-containing linear polymer of the present invention, when the number of the above-mentioned repeating units is appropriate and within the above-mentioned weight average molecular weight range, in addition to high alkali solubility, it also has the advantages of being able to achieve a practical softening point, coating properties, and coating film strength.

[0109] Furthermore, in the silicon-containing linear polymer of the present invention represented by the above structural formula (1), the single terminal group X is a hydroxyl group or a group represented by the following formula (3).

[0110] [Chemical formula 15]

[0111]

[0112] (Where R 1 ~R 3 is the above-mentioned group, and * is the bonding site with the carbonyl group. )

[0113] Here, the terminal group X is related to the ultraviolet curability of the linear polymer and is preferably a group represented by the above formula (3), which tends to provide higher ultraviolet curability.

[0114] Similarly, in the silicon-containing linear polymer of the present invention represented by the above structural formula (1), the other terminal group Y is a hydrogen atom or a group represented by the following formula (4).

[0115] [Chemical formula 16]

[0116]

[0117] (In the formula, A is the above-mentioned group, and * is the bonding site with the oxygen atom.)

[0118] Here, the terminal group Y is related to the ultraviolet curability of the obtained linear polymer as described above, and is preferably a hydrogen atom, which tends to provide higher ultraviolet curability.

[0119] [Method for producing silicon-containing linear polymer according to the present invention]

[0120] The method for producing the ultraviolet curable silicon-containing linear polymer of the present invention is not limited, but from the viewpoint of production efficiency, a method of reacting an organic silicon compound represented by the following formula (6) with a tetracarboxylic acid represented by the following formula (7a) or a tetracarboxylic dianhydride represented by the following formula (7b) is preferred.

[0121] [Chemical formula 17]

[0122]

[0123] (Where R 1 ~R 3 is the group mentioned above.)

[0124] [Chemical formula 18]

[0125]

[0126] [Chemical formula 19]

[0127]

[0128] The terminal hydroxyl group of the organosilicon compound represented by the above formula (6) forms an ester bond with two carboxyl groups in the compound represented by the formula (7a) or (7b) (a tetracarboxylic anhydride having four carboxyl groups or an anhydrous structure providing four carboxyl groups), thereby forming a partial structure (-C(=O)-AC(=O)O-) containing A in the repeating unit in the above structural formula (1). Therefore, in the above production method, Z as a tetracarboxylic acid residue, in other words, is a structure that provides a divalent linking group as the above A as a partial structure containing the remaining two carboxyl groups after the above ester bond formation reaction, and an example thereof is a residue obtained by removing two carboxyl groups from the divalent linking group as the above A. Preferably, the divalent residue is a divalent residue in which two carbon-hydrogen bonding sites are substituted with carbon-carboxyl bonding sites from an alkylene group, an arylene group, and an arylenealkylene group that optionally have an oxygen atom (the above 8a) or a carbonyl group (the above 8c) between carbon-carbon bonds.

[0129] Examples of the tetracarboxylic acid or its dianhydride include linear hydrocarbon tetracarboxylic acid or its dianhydride which may contain a heteroatom, alicyclic tetracarboxylic acid or its dianhydride which may contain a heteroatom, and aromatic tetracarboxylic acid or its dianhydride which may contain a heteroatom and a halogen atom.

[0130] Specific examples of the tetracarboxylic acid or its dianhydride include ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, dicyclohexyl-3, 4,3',4'-tetracarboxylic acid, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid-1,2,3,4-dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,2]octane-2,3 ,5,6-tetracarboxylic acid, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, pyromellitic acid, pyromellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic acid, 3,4 , 9,10-perylenetetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, diphenyl-2,3,3',4'-tetracarboxylic acid, diphenyl-2,3,3',4'-tetracarboxylic dianhydride, 4,4'-diphthalic acid, 4,4'-diphthalic anhydride, etc. These can be used alone or in combination of two or more compounds. From the viewpoint of the manufacturing efficiency of the linear polymer of the present invention, it is preferred to use an acid dianhydride. Among them, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, pyromellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride are preferably used, and 1,2,3,4-butanetetracarboxylic dianhydride is particularly preferably used.

[0131] On the other hand, the organosilicon compound represented by the above formula (6) is a compound containing two (meth)acrylate groups in the molecule and having alcoholic hydroxyl groups at both ends. 1 and a divalent linking group R 2 ~R4 As described above. In addition, there is no limitation on the method for producing the organosilicon compound. In a preferred embodiment, the organosilicon compound is produced by subjecting a molecule having a total of two groups containing a cyclic structure composed of carbon and oxygen, such as an epoxy group or an oxetane group, to an addition reaction with acrylic acid or methacrylic acid. Here, the organosilicon compound having a total of two epoxy groups or oxetane groups in the molecule may be an organosilicon compound represented by the following formula (9).

[0132] [Chemical formula 20]

[0133]

[0134] Here, R 1 and R 2 As above. 5 It is an epoxy-containing group or an oxetane-containing group, and specifically, examples thereof include a glycidoxyethyl group, a glycidoxypropyl group, an oxetaneethyl group, an oxetanepropyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, and a 3-(3,4-epoxycyclohexyl)propyl group. Among them, a glycidoxypropyl group and a 2-(3,4-epoxycyclohexyl)ethyl group can be used as preferred groups.

[0135] Preferred specific examples of the organosilicon compound represented by the above formula (9) include 1,3-diglycidoxypropyl-1,1,3,3-tetramethyldisiloxane, 1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]-1,1,3,3-tetramethyldisiloxane, 1,5-diglycidoxypropyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, and 1,5-bis[2-(3,4-epoxycyclohexyl)ethyl]-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane.

[0136] In a preferred embodiment, the organosilicon compound represented by the above formula (6) can be produced by an addition reaction of the organosilicon compound represented by the above formula (9) with acrylic acid or methacrylic acid in the presence of a basic compound as a catalyst, usually at a temperature range of 60 to 120° C. Here, as the basic compound, a generally known organic base can be used, and specifically, triethylamine, pyridine, N,N-dimethylaniline, 1,1,3,3-tetramethylguanidine, 1,8-diazabicyclo(5,4,0)undec-7-ene [DBU], 1,5-diazabicyclo(4,3,0)-5-nonene [DBN], triphenylphosphine, tetrabutylammonium bromide, tetrabutylphosphonium bromide, etc. can be used.

[0137] Furthermore, the reaction of the organosilicon compound represented by the above formula (6) and the acid dianhydride preferably represented by the above formula (7b) is carried out in the presence of the above basic compound, usually in a temperature range of 40 to 100°C, to produce the ultraviolet curable linear polymer of the present invention represented by the above formula (1). By adjusting the stoichiometric ratio of the organosilicon compound represented by the above formula (6) and the acid dianhydride preferably represented by the above formula (7b), the degree of polymerization, i.e., the molecular weight and the polymer terminal groups X and Y of the produced ultraviolet curable linear polymer can be controlled. The closer the stoichiometric ratio is to 1, the greater the degree of polymerization. In addition, the greater the stoichiometric ratio of the organosilicon compound, the easier it is for X to become the group represented by the above formula (3) and the easier it is for Y to become a hydrogen atom.

[0138] [Ultraviolet curable composition]

[0139] The ultraviolet curable composition of the present invention comprises (A) the ultraviolet curable silicon-containing linear polymer and (B) a photopolymerization initiator, and may optionally comprise (C) an organic solvent and (D) an ultraviolet curable branched polysiloxane.

[0140] [Ingredient (B)]

[0141] Component (B) is a component that catalyzes the curing reaction of component (A) caused by ultraviolet rays. Generally, a compound group known as a photopolymerization initiator can be used. In the present invention, a photoradical polymerization initiator can be used as a photopolymerization initiator. The photoradical polymerization initiator generates free radicals by irradiation with ultraviolet rays, and the free radicals can cause a free radical polymerization reaction to cure the composition of the present invention.

[0142] [Photoradical polymerization initiator]

[0143] It is known that photoradical polymerization initiators are roughly divided into photolysis type and hydrogen abstraction type, but the photoradical polymerization initiator used in the composition of the present invention can be arbitrarily selected from photoradical polymerization initiators known in the technical field and is not particularly limited to a specific photoradical polymerization initiator. Examples of photoradical polymerization initiators include: acetophenone, p-anisil, dibenzoyl, benzoin, benzophenone, 2-benzoylbenzoic acid, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, 4-benzoylbenzoic acid, 2, 2'-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2-benzoylbenzoic acid methyl ester, 2-(1,3-benzodioxolan-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-benzyl-2-(dimethylamino)-4'-morpholinophenyl butanone, (±)-camphorquinone, 2-chlorothioxanthone, 4,4'-dichlorobenzophenone , 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4-diethylthioxanthen-9-one, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, (2,4,6-trimethylbenzoyl) phenyl phosphinate ethyl ester, 1,4-dibenzoylbenzene, 2-ethylanthraquinone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-isopropylthioxanthone, phenyl (2,4,6-trimethylbenzoyl) phosphate lithium salt, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isonitrosopropiophenone, 2-phenyl-2-(p-toluenesulfonyloxy) acetophenone and phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, but are not limited to these. In addition, as the photoradical polymerization initiator, in addition to the above-mentioned compounds, initiators such as Omnirad (registered trademark) 651, 184, 1173, 2959, 127, 907, 369, 369E and 379EG (alkyl phenone-based photopolymerization initiators, IGM Resins BV), Omnirad (registered trademark) TPO H, TPO-L and 819 (acylphosphine oxide-based photopolymerization initiators, IGM RESINS B.V.), Omnirad (registered trademark) MBF and 754 (intramolecular hydrogen abstraction type photopolymerization initiators, IGM Resins BV), Irgacure (registered trademark) OXE01 and OXE02 (oxime ester-based non-associative polymerization initiators, BASF) can be listed.

[0144] The amount of the photoradical polymerization initiator added to the curable composition of the present invention is not particularly limited as long as it causes the target photopolymerization reaction or photocuring reaction. Generally, the photoradical polymerization initiator is used in an amount of 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of component (A) of the present invention. These polymerization initiators may be used alone or in combination of two or more polymerization initiators, for example, two or more polymerization initiators having different maximum absorption wavelength regions.

[0145] In addition, a photosensitizer can also be used in combination with the above-mentioned photo-radical polymerization initiator. It is known that the use of a sensitizer can improve the photon efficiency of the polymerization reaction, and compared with the case of using only a photopolymerization initiator, it becomes possible to use longer wavelength light in the polymerization reaction, so it is particularly effective when the coating thickness of the composition is thicker or when a longer wavelength LED light source is used. As a sensitizer, it is known that there are: anthracene compounds, phenothiazine compounds, perylene compounds, anthocyanin compounds, merocyanine compounds, coumarin compounds, benzylidene ketone compounds, (thio) xanthene or (thio) xanthone compounds, such as isopropyl thioxanthone, 2,4-diethyl thioxanthone, alkyl substituted anthracene, squarylium compounds, (thio) pyrylium compounds, porphyrin compounds, etc., but are not limited to these, and any photosensitizer can be used for the curable composition of the present invention.

[0146] [Organic solvents]

[0147] The ultraviolet curable composition of the present invention preferably contains (C) an organic solvent in order to adjust the coating properties and film thickness of the ultraviolet curable silicon-containing linear polymer as component (A), improve the dispersibility of the photopolymerization initiator, etc. As the organic solvent involved, organic solvents conventionally prepared in various ultraviolet curable compositions can be used without particular limitation.

[0148] Preferred examples of the organic solvent include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-n-butyl ether; and ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate and other (poly) alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 5-methyl-3-heptanone, 2,4-dimethyl-3-pentanone, 2,6-dimethyl-4-heptanone; methyl 2-hydroxypropionate, 2-hydroxy Lactic acid alkyl esters such as ethyl propionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate , n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate and other esters; aromatic hydrocarbons such as toluene, xylene, mesitylene, isopropylbenzene, propylbenzene, diethylbenzene, 1,3-diisopropylbenzene; aromatic ethers such as anisole, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 3,4-dimethoxytoluene, 1,4-bis(methoxymethyl)benzene. The organic solvent may be used alone, or a plurality of organic solvents may be used in combination in consideration of miscibility with component (A) and component (B).

[0149] The content of the organic solvent is not particularly limited and is appropriately set according to the miscibility with the ultraviolet curable silicon-containing linear polymer (A), the film thickness of the coating formed by the ultraviolet curable composition, etc. Typically, 50 to 10,000 parts by mass are used relative to 100 parts by mass of component (A). That is, when an organic solvent is used, the solute concentration of the ultraviolet curable silicon-containing linear polymer (A) in the ultraviolet curable composition of the present invention is preferably in the range of 1 to 66% by mass, and more preferably in the range of 2 to 40% by mass.

[0150] [Ingredient (D)]

[0151] Component (D) is a branched polysiloxane having ultraviolet curability and is an optional component added as needed. Component (D) has the function of adjusting the ultraviolet curability of component (A) and the viscosity of the entire curable composition, and on the other hand, controlling the mechanical properties of the cured product such as hardness and toughness.

[0152] The structure of component (D) is not limited, but preferably a branched polysiloxane having both a hydrophilic group and an ultraviolet curable group in one molecule and being soluble in an alkaline aqueous solution. Particularly preferably, a branched polysiloxane having one or more monovalent functional groups bonded to a silicon atom and having both a hydrophilic group and an ultraviolet curable group in one molecule and being soluble in an alkaline aqueous solution is used.

[0153] In a preferred embodiment, the ultraviolet curable branched polysiloxane preferably has one or more siloxane units selected from the following repeating units (11) and (12) in one molecule, particularly from the viewpoint of its alkali solubility.

[0154] (R 11 R 2 / 2 )(11)

[0155] (E 3 SiO 1 / 2 )(12)

[0156] (Where R 11 is a monovalent functional group having both a hydrophilic group and an ultraviolet curable group, R is a group selected from an unsubstituted or fluorine-substituted monovalent hydrocarbon group, an alkoxy group and a hydroxyl group, and E is R 11 or R, E contains at least one R 11 )

[0157] The organopolysiloxane preferably contains the siloxane unit (11). The siloxane unit provides a higher toughness and better transparency, especially for a thick coating, than a cured product consisting of only silsesquioxane units.

[0158] The organopolysiloxane may further contain the following siloxane unit (13). 12 It is a monovalent functional group having an ultraviolet curable group and having no hydrophilic group, and R is the above-mentioned group.

[0159] (R 12 RSiO)(13)

[0160] Here, the ultraviolet curable branched polysiloxane has a monovalent functional group bonded to a silicon atom and having both a hydrophilic group and an ultraviolet curable group. As the hydrophilic group in the monovalent functional group, a group selected from a carboxyl group, a hydroxyl group, a phenolic hydroxyl group, and a polyether group can be preferably used. Among them, a carboxyl group is most preferably used from the aspect of the effect of increasing alkali solubility.

[0161] Similarly, as the ultraviolet curable group in the monovalent functional group, a group selected from an epoxy group, an oxetane group, a vinyl ether group, and a (meth)acryloyloxy group can be preferably used. Among them, from the viewpoint of ease of manufacture and raw material availability, an epoxy group and a (meth)acryloyloxy group are more preferred, and a (meth)acryloyloxy group is most preferred.

[0162] In a preferred embodiment, the organopolysiloxane is composed of the average unit formula (14):

[0163] (G 3 SiO 1 / 2 ) a (R 11 R 2 / 2 ) b1 (R 12 R 2 / 2 ) b2 (RSiO 3 / 2 ) c (SiO 4 / 2 ) d (14)

[0164] The branched polysiloxane shown.

[0165] (Where R 11 , R 12 R and R are each independently the same group as above, and G is each independently selected from R, R 11 and R 12 a is 0 or a positive number, b1 is a number in the range of 1 to 100, b2 is a number in the range of 0 to 50, and (c+d) is a positive number)

[0166] In the branched polysiloxane represented by the above average unit formula (14), there is no restriction on the ratio of each constituent unit, but the lower limit of the value of (b1+b2) / (a+b1+b2+c+d) is preferably 0.1 or more, more preferably 0.15 or more. On the other hand, the preferred upper limit of this value is 0.5, more preferably 0.4 or less. By setting the ratio represented by the above formula within this range, the ultraviolet curability, alkali solubility and surface viscosity of the branched polysiloxane after coating on the substrate can be appropriately controlled.

[0167] The branched polysiloxane may further have a member selected from (RSiO3 / 2 ) and the T unit shown by (SiO 4 / 2 ) represented by the siloxane unit Q, in particular, may also have (RSiO 3 / 2 ) shown in the siloxane T unit.

[0168] As specific examples of the ultraviolet curable branched polysiloxanes preferably used, polysiloxanes composed of the following combinations of siloxy units can be exemplified. Here, M represents a trimethylsiloxy unit, M Vi represents dimethylvinylsiloxy unit, M R1 represents a siloxane unit having a monovalent group containing both a hydrophilic group and an ultraviolet curable group and two methyl groups, D represents a dimethylsiloxy unit, and D R1 represents a siloxane unit having a monovalent group containing both a hydrophilic group and an ultraviolet curable group and a methyl group, D R2 represents a siloxane unit having a monovalent group containing an ultraviolet curable group and a methyl group, T represents a siloxy unit, T R represents an alkylsiloxy unit (the alkyl group is a propyl group or a hexyl group), T Ph represents a phenylsiloxy unit, T R1 represents a siloxane unit having a monovalent group containing both a hydrophilic group and an ultraviolet curable group, and Q represents a siloxy unit having no organic group. It should be noted that in the following examples of combinations, the specific number of each siloxy unit is omitted.

[0169] Examples of preferred combinations of siloxy units constituting the ultraviolet curable branched polysiloxane include:

[0170] M R1 T Ph ,MM R1 T Ph 、M Vi M R1 T Ph 、M R1 DT Ph ,MM R1 DT Ph 、M Vi M R1 DT Ph 、M R1 Q.MM R1 Q.M Vi M R1 Q.M R1 DQ, MM R1 DQ, M Vi M R1 DQ, M R1 T.MMR1 T、M Vi M R1 T、M R1 TT R 、MM R1 TT R 、M Vi M R1 TT R 、M R1 DT、MM R1 DT、M Vi M R1 DT、M R1 DTT R 、MM R1 DTT R 、M Vi M R1 DTT R 、MD R1 T、MD R1 D R2 T、D R1 T、D R1 D R2 T、D R1 T R 、D R1 D R2 T R 、MD R1 TT R 、MD R1 D R2 TT R 、MD R1 T R 、MD R1 D R2 T R 、D R1 TT R 、D R1 D R2 TT R 、MD R1 T Ph 、MD R1 D R2 T Ph 、D R1 T Ph 、D R1 D R2 T Ph 、D R1 T Ph Q、D R1 D R2 T Ph Q、MD R1 Q、MD R1 D R2 Q、M Vi DR1 Q.M Vi D R1 D R2 Q

[0171] The substituent R in the branched polysiloxane is a group selected from unsubstituted or fluorine-substituted monovalent hydrocarbon groups, alkoxy groups and hydroxyl groups. The unsubstituted or fluorine-substituted monovalent hydrocarbon group is preferably a group selected from unsubstituted or fluorine-substituted alkyl groups, cycloalkyl groups, arylalkyl groups and aryl groups having 1 to 20 carbon atoms. As the above-mentioned alkyl group, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, pentyl, hexyl and octyl can be listed, but methyl and hexyl are particularly preferred. As the above-mentioned cycloalkyl group, cyclopentyl and cyclohexyl can be listed. As the above-mentioned arylalkyl group, benzyl and phenethyl can be listed. As the above-mentioned aryl group, phenyl and naphthyl can be listed. As examples of the monovalent hydrocarbon group substituted by fluorine, 3,3,3-trifluoropropyl and 3,3,4,4,5,5,6,6,6-nonafluorohexyl can be listed, but 3,3,3-trifluoropropyl is preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

[0172] The substituent R described in formula (11) etc. 11 It is a monovalent functional group bonded to a silicon atom and having both a hydrophilic group and an ultraviolet curable group.

[0173] As the monovalent functional group (especially the substituent R 11 ), preferably a group represented by the following formula (15).

[0174] [Chemical formula 21]

[0175]

[0176] {In the formula, R 14 is a chain divalent hydrocarbon group having 2 to 10 carbon atoms, R 15 is a trivalent hydrocarbon group having 3 to 10 carbon atoms, in the form of a chain, a ring, or a combination thereof, and L is an oxygen atom, a sulfur atom, or -NR 17 -(where R 17 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms), m is 0 or 1, Q is a group containing a monovalent ultraviolet curable group, J is a hydroxyl group or -O(C=O)-R 16 -CO 2 H(where R 16 is a monovalent hydrophilic group represented by a linear, branched or cyclic divalent hydrocarbon group having 2 to 12 carbon atoms which may optionally contain an oxygen atom or a sulfur atom, and * is a bonding site with a silicon atom on the polysiloxane.

[0177] Linking group R 14The chain divalent hydrocarbon group having 2 to 10 carbon atoms includes ethylene, propylene, butene, hexene and the like, and ethylene and propylene are preferred.

[0178] The linking group L is an oxygen atom, a sulfur atom or NR 17 In addition, R 17 It is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms.

[0179] On the other hand, the linking group R 15 It is a trivalent hydrocarbon group having 3 to 10 carbon atoms in a chain, a ring or a combination thereof, i.e., an alkanetriyl group. Examples thereof include propylenetriyl, butyltriyl, hexanetriyl, octanetriyl, ethylcyclohexanetriyl, propylcyclohexanetriyl, etc., but propylenetriyl and ethylcyclohexanetriyl of the following structural formula (16) can be used as preferred linking groups.

[0180] [Chemical formula 22]

[0181]

[0182] (Wherein, * indicates the bonding site)

[0183] The above Q is a group containing a monovalent ultraviolet curable group. As the ultraviolet curable group that can be used, epoxy, oxetane, vinyl ether, (meth) acryloyloxy, etc. can be listed, and (meth) acryloyloxy is a preferred ultraviolet curable group. Therefore, the preferred examples of Q are acryloyloxy and methacryloyloxy.

[0184] The above-mentioned J is a hydrophilic group, preferably a hydroxyl group, a hydroxyl group-containing group, or a carboxyl group-containing group. As the hydroxyl group-containing group, an alcoholic hydroxyl group or a phenolic hydroxyl group bonded by a divalent linking group can be used. 2 Such J is selected from hydroxyl, hydroxyl-containing groups or -O(C=O)-R 16 -CO 2 One or more types of monovalent hydrophilic groups represented by H.

[0185] The above-mentioned linking group R 16 It is a divalent hydrocarbon group that may optionally contain an oxygen atom or a sulfur atom as a heteroatom, specifically, a linear, branched or cyclic divalent hydrocarbon group having 2 to 12 carbon atoms; a sulfur-containing linear, branched or cyclic divalent hydrocarbon group; an oxygen-containing linear, branched or cyclic divalent hydrocarbon group. More specifically, the divalent groups exemplified by the following structural formula (17) can be listed. Among them, 16a, 16b, 16c, 16d, 16e, 16i, 16k, 16m, 16p, 16q, 16r, and 16s can be preferably used.

[0186] [Chemical formula 23]

[0187] *-CH 2 CH 2 -* *-CH 2 CH 2 CH 2 -* *-CH 2 OCH 2 -* *-CH 2 SCH 2 -*

[0188]

[0189] (Wherein, * indicates the bonding site)

[0190] On the other hand, the substituent R 12 It is a monovalent group having an ultraviolet curable group and having no hydrophilic group. As the ultraviolet curable group, a group selected from an epoxy group, an oxetane group, a vinyl ether group, and a (meth)acryloyloxy group can be preferably used. As mentioned above, an epoxy group and a (meth)acryloyloxy group are more preferred. Therefore, as R 12 Specific examples include a glycidoxyethyl group, a glycidoxypropyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-(epoxycyclohexyl)propyl group, an acryloxypropyl group, a methacryloxypropyl group, an acryloxyoctyl group, and a methacryloxyoctyl group.

[0191] As the ultraviolet curable branched polysiloxane, a branched polysiloxane having monovalent functional groups of (meth)acryloyloxy and carboxyl groups bonded to silicon atoms is recommended. In order to give the polysiloxane good ultraviolet curability and excellent alkali solubility, the monovalent functional groups preferably have an average of 2.5 or more in each molecule.

[0192] The molecular weight of the ultraviolet curable branched polysiloxane is not particularly limited, but in consideration of coating properties and mechanical strength characteristics of the coated film, the weight average molecular weight in terms of polystyrene determined by gel permeation chromatography is preferably 1,000 to 100,000, more preferably 1,000 to 10,000.

[0193] The cured product obtained by the ultraviolet curable composition of the present invention can be based on the molecular structure of component (A), i.e. the chemical structure and polymerization degree of the main chain, in addition, according to the molecular structure and addition of component (B) and the molecular structure and addition of any added component (D), the physical properties of the desired cured product and the curing speed of the curable composition can be obtained, and further, according to the deployment amount of component (C), the viscosity of the curable composition can be designed to a desired value. In addition, the cured product obtained by curing the ultraviolet curable composition of the present invention is also included in the scope of the present invention. The shape of the cured product obtained by the curable composition of the present invention is not particularly limited, and can be a film-like coating, or a sheet-like molding, and can also be used as a sealing material, an intermediate layer of a laminate or a display device, etc. The cured product obtained by the composition of the present invention is preferably in the form of a film-like coating, and is particularly preferably a film-like insulating coating.

[0194] The ultraviolet curable composition of the present invention is suitable for use as a coating agent, particularly as an insulating coating agent for electronic devices and electric equipment.

[0195] [Other additives]

[0196] In addition to the above-mentioned components, further additives may be added to the composition of the present invention as desired. Examples of the additives include the following, but are not limited thereto.

[0197] [Thickener]

[0198] In the ultraviolet curable composition of the present invention, in order to improve the adhesion or the closeness relative to the base material contacted with the composition, an adhesion promoter can be added. When the curable composition of the present invention is used for the coating agent, sealing material, etc., the adhesion or the closeness of the base material needs to be used, preferably in the curable composition of the present invention, a tackifier is added. As this adhesion promoter, as long as the curing reaction of the composition of the present invention is not hindered, any known adhesion promoter can be used.

[0199] Examples of adhesion promoters that can be used in the present invention include: organic silanes having trialkoxysilyloxy groups (e.g., trimethoxysilyloxy groups, triethoxysilyloxy groups) or trialkoxysilylalkyl groups (e.g., trimethoxysilylethyl groups, triethoxysilylethyl groups) and hydrosilyl groups or alkenyl groups (e.g., vinyl groups, allyl groups), or organic siloxane oligomers having a linear structure, a branched structure, or a cyclic structure having about 4 to 20 silicon atoms; organic silanes having trialkoxysilyloxy groups or trialkoxysilylalkyl groups and a methacryloxyalkyl group (e.g., 3-methacryloyloxy groups, oxypropyl) or an organosiloxane oligomer having a linear structure, branched structure or cyclic structure with about 4 to 20 silicon atoms; an organosilane having a trialkoxysilyloxy group or a trialkoxysilylalkyl group and an epoxy-bonded alkyl group (for example, 3-glycidoxypropyl, 4-glycidoxybutyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl) or an organosiloxane oligomer having a linear structure, branched structure or cyclic structure with about 4 to 20 silicon atoms; an organosilane having two or more trialkoxysilyl groups (for example, trimethoxy Silane group, triethoxysilane group) organic compound; aminoalkyltrialkoxysilane and epoxy-bonded alkyltrialkoxysilane reaction products, epoxy-containing ethyl polysilicate, specifically, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hydrogentriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 1,6 -Bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,3-bis[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane, a reaction product of 3-glycidoxypropyltriethoxysilane and 3-aminopropyltriethoxysilane, a condensation reaction product of a silanol-terminated methylvinylsiloxane oligomer and 3-glycidoxypropyltrimethoxysilane, a condensation reaction product of a silanol-terminated methylvinylsiloxane oligomer and 3-methacryloxypropyltriethoxysilane, and tris(3-trimethoxysilylpropyl)isocyanurate.

[0200] The amount of the adhesion promoter added to the ultraviolet curable composition of the present invention is not particularly limited, but is preferably in the range of 0.01 to 5 parts by mass, or in the range of 0.01 to 2 parts by mass, relative to 100 parts by mass of component (A), from the perspective of the curing characteristics of the curable composition and not promoting discoloration of the cured product.

[0201] [Further optional additives]

[0202] In the ultraviolet curable composition of the present invention, other additives may be added as required in addition to or in place of the above-mentioned adhesion imparting agent. As the additive that can be used, leveling agents, silane coupling agents, ultraviolet light absorbers, antioxidants, polymerization inhibitors, fillers (functional fillers such as reinforcing fillers, insulating fillers and thermally conductive fillers) etc. that are not included in the material listed as the above-mentioned adhesion imparting agent may be listed. As required, suitable additives may be added in the composition of the present invention. In addition, in the composition of the present invention, as required, particularly when used as a sealing material, a thixotropic imparting agent may be added.

[0203] [Method for producing cured film]

[0204] The method for producing the cured film is not particularly limited as long as it is a method that can cure the film composed of the above-mentioned ultraviolet curable composition. A well-known photolithography process can be applied, and a patterned cured film is preferably produced. As a typical production method, a method comprising the following steps is recommended:

[0205] 1) Forming a coating film of the ultraviolet curable composition on a substrate.

[0206] 2) The obtained coating film is heated at a temperature of about 100° C. or less for a short time to remove the solvent.

[0207] 3) Perform position selective exposure on the coating film.

[0208] 4) Developing the exposed coating film.

[0209] 5) The patterned cured film is heated at a temperature exceeding 100° C. to completely cure the film.

[0210] The above-mentioned manufacturing method is described in detail.

[0211] The substrate is not particularly limited, and various substrates such as a glass substrate, a silicone substrate, and a glass substrate coated with a transparent conductive film can be used.

[0212] In order to apply the ultraviolet curable composition onto a substrate, a known method using a coating device such as a spin coater, a roll coater, a bar coater, or a slit coater can be applied.

[0213] The applied curable composition is heated, dried, and the solvent is removed as necessary. Typically, the method includes drying on a hot plate at 80 to 120° C., preferably 90 to 100° C. for 1 to 2 minutes, leaving it at room temperature for several hours, and heating it in a hot air heater or infrared heater for several tens of minutes to several hours.

[0214] The position-selective exposure of the coating film is usually performed through a photomask or the like, using a known active energy line light source including ultraviolet light sources such as high-pressure mercury lamps, metal halide lamps, LED lamps, and laser light sources such as excimer lasers. Depending on the characteristics of the curable composition, negative and positive photomasks can be used. The energy dose irradiated depends on the structure of the curable composition, but is typically about 100 to 1,000 mJ / cm2.

[0215] In order to form a pattern of a desired shape, a developer is used for development. As a developer, alkaline aqueous solutions and organic solvents are known, but alkaline aqueous solutions are mainly used for development. Alkaline aqueous solutions can use both aqueous solutions of inorganic alkalis and aqueous solutions of organic alkalis. As preferred developers, alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts can be listed, and aqueous solutions of tetramethylammonium hydroxide (TMAH) are particularly preferred. The developing method is not particularly limited, and for example, an immersion method, a spray method, etc. can be applied.

[0216] As described above, the UV-curable linear polymer and the UV-curable composition containing the same as the main component according to the present invention have excellent UV curability and, on the other hand, have remarkably excellent alkali solubility. Therefore, particularly when subjected to a development step using an alkaline aqueous solution, they have the advantages that a simple and high-precision pattern can be formed and the obtained cured film has excellent mechanical strength and transparency.

[0217] The patterned cured film after development is usually preferably subjected to a heat treatment (post-exposure baking [PEB]). The PEB temperature is not particularly limited as long as the patterned cured film does not undergo thermal decomposition or deformation, but is preferably 100 to 200°C, more preferably 100 to 150°C. In addition, the heat treatment time is arbitrary, but is usually 1 to 1.5 minutes.

[0218] By the above operation, a cured film of the ultraviolet curable composition patterned into a desired shape can be formed.

[0219] [use]

[0220] The ultraviolet curable composition of the present invention is particularly useful as a material for forming an insulating layer constituting various articles, particularly electronic devices and electrical equipment. The composition can be designed to have a low relative dielectric constant of less than 3.0 after curing. In addition, with respect to the curable composition of the present invention, the transparency of the cured product obtained therefrom is good, and therefore it is particularly suitable as a material for forming an insulating layer of a display device such as a touch panel and a display. In this case, the insulating layer can also form a desired optional pattern as described above as required. Therefore, a display device such as a touch panel and a display including an insulating layer obtained by curing the ultraviolet curable composition of the present invention is also a mode of the present invention.

[0221] In addition, after applying the curable composition of the present invention to an article, it is cured to form an insulating coating (insulating film). Therefore, the composition of the present invention can be used as an insulating coating agent. In addition, the cured product formed by curing the curable composition of the present invention can also be used as an insulating coating.

[0222] The insulating film formed by the curable composition of the present invention can be used for various purposes other than the above-mentioned display device. In particular, it can be used as a component of an electronic device, or can be used as a material used in the process of manufacturing an electronic device. The electronic device includes electronic devices such as semiconductor devices and magnetic recording heads. For example, the curable composition of the present invention can be used as a semiconductor device, such as LSI (Large Scale Integration), system LSI, DRAM (Dynamic Random Access Memory), SDRAM (Synchronous Dynamic Random Access Memory), RDRAM (Rambus Dynamic Random Access Memory), D-RDRAM (Direct Rambus Dynamic Random Access Memory) and multi-chip module (Multichip Module) multilayer wiring board insulation coating, semiconductor interlayer insulation film, etching stopper (Etching Stopper) film, surface protection film, buffer coating, passivation film in LSI, cover coat of flexible copper clad board, solder resist film, surface protection film for optical device.

[0223] Hereinafter, the present invention will be further described based on examples, but the present invention is not limited to the following examples.

[0224] Example

[0225] The synthesis of the ultraviolet curable silicon-containing linear polymer of the present invention, the preparation / evaluation of the ultraviolet curable composition, and the preparation / evaluation of the cured product thereof are described in detail by way of examples. It should be noted that in the structural formula, Me is a methyl group and Ph is a phenyl group.

[0226] [Appearance of UV-curable composition and cured product]

[0227] The ultraviolet curable composition and the cured product were visually observed to determine their appearance.

[0228] [Softening point of UV-curable silicon-containing linear polymer]

[0229] A 25 mass % PGMEA solution of each curable linear polymer was spin-coated on an optical glass to a film thickness of about 4.0 μm, and heated (prebaked) at 100° C. for 2 minutes using a hot plate to form a coating film. The obtained coating film was heated in an oven preheated to 50° C. for 5 minutes, and the softening point was evaluated according to the following criteria.

[0230] A: The surface state of the coating does not change, and there is no stickiness (softening point is above 50°C)

[0231] B: The coating is softened and has surface stickiness (softening point is below 50°C)

[0232] [Alkali Solubility of UV Curable Silicon-Containing Straight Chain Polymer and UV Curable Composition]

[0233] The coating films of each silicon-containing linear polymer and each curable composition shown in Table 2 below were prepared by the above method. Then, the coating films were developed at 25°C using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute, and then immersed in a water bath at room temperature (25°C) for washing. The washing time was 15 seconds. After washing, the water was removed by drying, and the glass substrate was visually observed to determine the solubility (developability) in the alkaline solution according to the following criteria.

[0234] A: Completely dissolved: The coating is completely removed

[0235] B: Almost dissolved: A small amount of coating film residue (scum) was observed

[0236] C: Partial dissolution: A large amount of scum (more than 20% of the coating area) was observed

[0237] D: Insoluble

[0238] [Ultraviolet curability of curable composition]

[0239] The coating films of each curable composition shown in Table 2 below prepared by the above method were irradiated with ultraviolet light (365 nm LED light, 500 mJ / cm2) and further heated at 100°C for 2 minutes (post-baking) to obtain cured coating films. The ultraviolet curability was judged according to the following criteria.

[0240] A: The cured coating is insoluble in the above TMAH dissolution test.

[0241] B: Only the edge portion of the cured coating (less than 5% of the total area of ​​the cured film) dissolved in the above TMAH dissolution test

[0242] C: The cured coating film is completely dissolved or almost dissolved in the above TMAH dissolution test

[0243] [Synthesis Example 1] Synthesis of a hydroxyl-functional organosilicon compound (A-1) containing acrylate groups at both ends

[0244] In a 500 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 138 g of 1,5-di(glycidoxypropyl)-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, 45 g of toluene, 37.2 g of acrylic acid, 0.12 g of dibutylhydroxytoluene, and 0.8 g of 1,1,3,3-tetramethylguanidine were added, and stirred at 90°C for 24 hours. Then, the reaction solution was allowed to cool to room temperature, diluted with 100 g of toluene, neutralized with an aqueous sodium bicarbonate solution, and washed with water three times. The volatile compounds were removed under reduced pressure to obtain a light yellow high-viscosity liquid. From the product 13 The C-NMR measurement results confirmed that the product was an acrylate group-containing dual-terminal hydroxyl-functional organic silicon compound having two acrylate groups in the molecule, which was obtained by addition reaction of acrylic acid and glycidoxy group.

[0245] [Synthesis Example 2] Synthesis of a hydroxyl-functional organosilicon compound (A-2) containing acrylate groups at both ends

[0246] The reaction was carried out in the same manner as in Synthesis Example 1 except that 50.2 g of 1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]-1,1,3,3-tetramethyldisiloxane was used in place of 138 g of 1,5-bis(glycidoxypropyl)-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane and the amounts of acrylic acid, toluene, dibutylhydroxytoluene and 1,1,3,3-tetramethylguanidine used were 19.8 g, 25 g, 0.6 g and 0.45 g, respectively, to obtain a light yellow high-viscosity liquid. 13 The C-NMR measurement results confirmed that the product was an acrylate group-containing dual-terminal hydroxyl-functional organic silicon compound having two acrylate groups in the molecule, which was produced by addition reaction of acrylic acid and epoxy groups.

[0247] [Synthesis Example 3 (Example)] Synthesis of linear polymer (A-3)

[0248] In a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 21.3 g of the above-mentioned organosilicon compound (A-1), 50 g of propylene glycol monomethyl ether acetate (PGMEA), 4.0 g of 1,2,3,4-butanetetracarboxylic acid-1,2,3,4-dianhydride, and 0.12 g of triphenylphosphine were added, and stirred at 110°C for 6 hours. The reaction solution was allowed to cool to room temperature, and the insoluble matter was filtered to obtain a polymer solution with a solid content concentration of about 33%. 13 The C-NMR measurement results confirmed that the product was a linear polymer (A-3) having two acrylate groups, two carboxyl groups and two siloxane bonds in the repeating unit, in which the terminal hydroxyl group reacted with the anhydride group. The analysis results of gel permeation chromatography showed that the Mn, Mw and PDI of (A-3) were 2,400, 4,680 and 1.95, respectively. These analysis results showed that the average number of repeating units of the linear polymer was 2, and each molecule had an average of six acrylate groups and an average of four carboxyl groups, and had the structure shown in the following A-3.

[0249] [Chemical formula 24]

[0250]

[0251] [Synthesis Example 4 (Example)] Synthesis of linear polymer (A-4)

[0252] The reaction was carried out in the same manner as in Synthesis Example 3 except that 20.5 g of the organosilicon compound (A-2), 5.15 g of 1,2,3,4-butanetetracarboxylic acid-1,2,3,4-dianhydride, 50 g of PGMEA and 0.15 g of triphenylphosphine were used instead of 21.3 g of the organosilicon compound (A-1). The reaction solution was allowed to cool to room temperature, and the insoluble matter was filtered to obtain a polymer solution having a solid content concentration of about 34%. 13 The C-NMR measurement results confirmed that the product was a linear polymer (A-4) having two acrylate groups, two carboxyl groups and one siloxane bond in the repeating unit, in which the terminal hydroxyl group reacted with the anhydride group. The analysis results of gel permeation chromatography showed that the Mn, Mw and PDI of (A-4) were 1,900, 4,700 and 2.47, respectively. These analysis results showed that the linear polymer had an average of 2 repeating units, and each molecule had an average of six acrylate groups and an average of four carboxyl groups, and had the structure shown in the following A-4.

[0253] [Chemical formula 25]

[0254]

[0255] [Synthesis Example 5 (Example)] Synthesis of linear polymer (A-5)

[0256] The reaction was carried out in the same manner as in Synthesis Example 3 except that 12.0 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 80 g of PGMEA and 0.22 g of triphenylphosphine were used instead of 39.6 g of the above-mentioned organosilicon compound (A-1) and 4.0 g of 1,2,3,4-butanetetracarboxylic acid-1,2,3,4-dianhydride. The reaction solution was allowed to cool to room temperature, and the insoluble matter was filtered to obtain a polymer solution having a solid content concentration of about 39%. 13 The C-NMR measurement results confirmed that the product was a linear polymer (A-5) having two acrylate groups, two carboxyl groups and two siloxane bonds in the repeating unit, in which the terminal hydroxyl group reacted with the anhydride group. The analysis results of gel permeation chromatography showed that the Mn, Mw and PDI of (A-5) were 2,700, 5,500 and 2.04, respectively. These analysis results showed that the linear polymer had an average of 2 repeating units, and each molecule had an average of six acrylate groups and an average of four carboxyl groups, and had the structure shown in the following A-5 [wherein, the CO residues were ignored] 2 The isomers are produced by the bonding position of the H group to the polymer main chain (i.e., the combination of 3,4 position and 3',4' position).

[0257] [Chemical formula 26]

[0258]

[0259] [Synthesis Example 6: Reference Example] Synthesis of branched polysiloxane (D-1) having acrylate groups and carboxyl groups

[0260] In a 200 mL separatory flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux tube, 37.55 g of a PGMEA solution of a branched polysiloxane containing an acrylate group represented by the following formula (19), 1.9 g of succinic anhydride and 0.32 g of 1,1,3,3-tetramethylguanidine were added, and the mixture was stirred at 70°C for 3 hours. Then, the reaction solution was allowed to cool to room temperature, 1.0 g of an alkaline adsorbent (KYOWARD (registered trademark) KW-700PL) was added, and the mixture was stirred for 30 minutes. The obtained solution was filtered, and the solid content concentration was prepared to 46%, to obtain a solution of a branched polysiloxane (D-1) having an acrylate group and a carboxyl group. From the product 13 As a result of C-NMR measurement, it was confirmed that the ratio of the structural unit containing an acrylate group and a carboxyl group to the structural unit containing a phenyl group in the obtained polysiloxane was 25:75 (the following structural formula D-1).

[0261] [R(CH 3 )SiO 2 / 2] 0.25 [(C 6 H 5 )SiO 3 / 2 ] 0.75 (19)

[0262] R is -(CH 2 ) 3 OCH 2 CH(OH)[CH 2 O(C=O)CH=CH 2 ]

[0263] [Chemical formula 27]

[0264]

[0265] Table 1 below shows the results of evaluating the softening points of linear polymers A-3 to A-5 according to Examples of the present invention by the above method.

[0266] [Table 1]

[0267] Linear polymer A-3 A-4 A-5 Features: Softening point B A A

[0268] [Examples 1 to 4 and Comparative Example 1]

[0269] The following linear polymer and curing catalyst were mixed according to the composition shown in Table 2 (parts by mass; (A) component and (D) component were converted to solid content), and then diluted with PGMEA to make the overall solid content concentration 25% by mass, and then filtered using a membrane filter with a pore size of 0.2 μm to prepare each UV curable composition. The appearance of these curable compositions, UV curability, appearance of the cured product, and the evaluation results of the alkali solubility of each polymer / curable composition are shown in Table 2.

[0270] (A-3) PGMEA solution of the ultraviolet curable silicon-containing linear polymer obtained in Synthesis Example 3

[0271] (A-4) PGMEA solution of the ultraviolet curable silicon-containing linear polymer obtained in Synthesis Example 4

[0272] (A-5) PGMEA solution of the ultraviolet curable silicon-containing linear polymer obtained in Synthesis Example 5

[0273] (A-1) The functional organosilicon compound obtained in the above-mentioned Synthesis Example 1

[0274] (D-1) PGMEA solution of polysiloxane having acrylate group and carboxyl group represented by the above structural formula (D-1) obtained in the above synthesis example 6

[0275] (B-1) Irgacure (registered trademark) OXE-02 manufactured by BASF

[0276] (B-2) Omnirad (registered trademark) 819 manufactured by IGM Resin

[0277] (C) PGMEA (organic solvent: propylene glycol monomethyl ether acetate)

[0278] [Table 2]

[0279]

[0280]

[0281] As shown in Table 2, the coating film formed by the ultraviolet curable straight-chain polymer of the present invention and the curable composition containing it shows high alkali solubility. In addition, the polymer involved in the present invention has good ultraviolet curability due to the appropriateness of its structure even if a multifunctional polymerizable monomer is not used. On the other hand, in the linear polymer (such as A-5) with insufficient ultraviolet curability, by mixing with other branched polysiloxanes (D-1) having acrylate groups and carboxyl groups, excellent curability can be achieved even without allocating multifunctional polymerizable monomers. In either case, the polymer involved in the present invention can provide a cured product with a high content of silicon-containing components. Further, it was confirmed that the cured coating film formed by ultraviolet irradiation is transparent, and in addition to the high transparency of the linear polymer itself, the affinity for the branched polysiloxanes having acrylate groups and carboxyl groups is also good. On the other hand, the linear polymer (Comparative Example 1) having an ultraviolet curable group and not having a hydrophilic group has poor alkali solubility and is not suitable as a patterning material.

[0282] Industrial Applicability

[0283] As described above, the ultraviolet curable linear polymer and the ultraviolet curable composition mainly composed of the ultraviolet curable polymer according to the present invention have excellent ultraviolet curability even without using a multifunctional polymerizable monomer. On the other hand, due to the significantly excellent alkali solubility, especially in the case of a development process using an alkaline aqueous solution, it has the following advantages: a simple and high-precision pattern can be formed, and the mechanical strength and transparency of the obtained cured film are excellent, and the content of the silicon-containing component can be designed to be high. Therefore, the linear polymer is particularly suitable as a material for forming an insulating layer of a display device such as a touch panel and a display, especially a flexible display, especially a patterning material and a coating material.

Claims

1. An ultraviolet curable silicon-containing linear polymer having two (meth)acrylate groups, two carboxyl groups and at least two silicon atoms in a repeating unit, and the polymer as a whole is soluble in an alkaline aqueous solution.

2. The ultraviolet curable silicon-containing linear polymer according to claim 1, which is represented by the following structural formula (1). According to the structural formula (1): [Chemical formula 1] (Where R 1 is an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 2 is a divalent linking group selected from an oxygen atom (—O—), a divalent hydrocarbon group having 1 to 10 carbon atoms, or a silicon-containing group represented by the following formula (2), R 3 Each of the following is a divalent linking group having one (meth)acrylate group, the number of carbon atoms in the part other than the (meth)acrylate group is 5 to 10 and may contain a heteroatom, A is a divalent linking group having two carboxyl groups, X is a hydroxyl group or a group represented by the following formula (3), Y is a hydrogen atom or a group represented by the following formula (4), and the number of repeating units n is a number in the range of 1 to 100) [Chemical formula 2] (OSiR 1 2 ) p ABOUT (2) (Where R 1 is the group described above, and p is a number from 1 to 20) [Chemical formula 3] (Where R 1 ~R 3 is the group, * is the bonding site with the carbonyl group) [Chemical formula 4] (wherein A is the group described above, and * is the bonding site with the oxygen atom) 3. The ultraviolet curable silicon-containing linear polymer according to claim 2, in, The R 3 The following structural formula 5a ~ 5d More than one divalent linking group is shown. [Chemical formula 5] (Where R 4 is a hydrogen atom or a methyl group, * is a site bonded to a silicon atom, and ** is a site bonded to an oxygen atom) 4. The ultraviolet curable silicon-containing linear polymer according to claim 2, in, The R 2 It is a divalent linking group selected from an oxygen atom (—O—) and a silicon-containing group represented by the above formula (2).

5. The ultraviolet curable silicon-containing linear polymer according to claim 2, in, The X is a group represented by the above formula (3), and the Y is a hydrogen atom.

6. The ultraviolet curable silicon-containing linear polymer according to claim 2, in, The n is a number in the range of 2-20.

7. The ultraviolet curable silicon-containing linear polymer according to claim 2, in, The A is a divalent linking group that does not contain an aromatic group.

8. The ultraviolet curable silicon-containing linear polymer according to claim 1, in, When a UV-curable linear polymer is applied on a glass plate in a manner to have a thickness of 4 μm after coating, and the coating is then immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute and then washed with water, the coating composed of the UV-curable linear polymer has a solubility in an alkaline aqueous solution with a mass reduction rate of 90% by mass or more.

9. A method for producing a UV-curable silicon-containing linear polymer, the UV-curable silicon-containing linear polymer according to claim 1, the method comprising the step of reacting an organosilicon compound represented by the following formula (6) with a tetracarboxylic acid represented by the following formula (7a) and a tetracarboxylic dianhydride represented by the following formula (7b). [Chemical formula 6] (Where R 1 ~R 3 is the group and number) [Chemical formula 7] [Chemical formula 8] (wherein Z is a tetracarboxylic acid residue) 10. An ultraviolet curable composition comprising: (A) the ultraviolet curable silicon-containing linear polymer according to any one of claims 1 to 8; and (B) A photopolymerization initiator in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the component (A). 11 . An insulating coating agent comprising the ultraviolet curable composition according to claim 10 .

12. A cured product of the ultraviolet curable composition according to claim 10.

13. A method of using a cured product of the ultraviolet curable composition according to claim 10 as an insulating coating. 14 . A display device comprising a layer composed of a cured product of the ultraviolet curable composition according to claim 10 .

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