TWI483955B - Α-allyloxymethyl methacrylate copolymer, resin composition and use thereof - Google Patents

Description

--allyloxy methacrylic copolymer, resin composition and use thereof

The present invention relates to an α-allyloxy methacrylic acid copolymer, a resin composition containing the same, and use thereof, and further relates to a method for producing the polymer. More specifically, the present invention relates to an α-allyloxy methacrylic copolymer which can be suitably used for various applications such as a radical curable resin composition, a colored material dispersion composition, and a photosensitive resin composition. These resin compositions, and methods of producing the polymers.

A resin (polymer) having a ring structure in the main chain is excellent in durability, particularly heat resistance, and is a useful material used in various fields of engineering plastics to optical materials or resist materials, and in particular, in recent years, research is underway. This is applied to various resin compositions such as a radical curable resin composition, a colored material dispersion composition, and a photosensitive resin composition, and is applied to a coating material, a high-functional ink, and a resist material.

The curable resin composition is used in various industrial fields, in which the radically curable resin composition composed of a radical polymerizable monomer and a binder resin is fast in curing speed, durability of the formed chemical bond, and economy. Excellent in terms of properties, etc., so it is used in a wide range of applications, such as coating materials, adhesives, sealing materials, adhesives, coatings, inks, resists, dental materials, lenses, molding materials, and the like.

On the other hand, the alkali-soluble resin is a material used in various industrial fields of civil engineering materials to electronic information materials, and one of its main uses is an alkali developing type resist.

The alkali-developing type resist (hereinafter sometimes simply referred to as a resist) is usually a resin composition containing an alkali-soluble resin, a hardening component, a photoinitiator for curing the hardening component, and a solvent. Useful industrial materials that are indispensable in the shadow technology, and various resistants such as solder resists, etching resistors, interlayer insulating materials, plating resists, and color filter resists depending on the application. Among them, the color filter resist is one of the resists required to have the highest level and various functions.

The color filter is a main component constituting a color liquid crystal display panel or a color image pickup tube element, and has a fine coloring layer for separating colors, whereby colorization of the liquid crystal display panel or the image pickup tube element can be realized. As a method of forming the colored layer, the following method is mainly used: an alkaline development type photosensitive film containing an alkali-soluble resin, a radical polymerizable monomer, a photoinitiator, a colored material as a coloring component, and a dispersing agent of a colored material. The resin composition (hereinafter sometimes referred to as a coloring resist) forms a coloring layer by photolithography. In the production of a color filter or a liquid crystal display panel, the step of applying a temperature exceeding 200 ° C is repeatedly performed, and the color layer of the color filter is required to withstand the heat resistance of the heat history. Further, in recent years, in order to improve the display quality or the image quality, the color toner is more stringent in color purity, and the concentration of the colored material in the coloring resist tends to increase. However, the high concentration of the colored material in the coloring resist causes the dispersion stability of the colored material and the plate-making property of the coloring resist (coatability, hardenability, development residue, development time, edge shape, dry resolubility, etc.) )decline. If the amount of the dispersant is increased in order to ensure the dispersion stability of the colored material, the amount of the radical polymerizable monomer and the alkali-soluble resin must be reduced to a corresponding extent, so that not only the plate-making property of the coloring resist but also the heat resistance is lowered. The tendency (heat-resistant decomposition property, heat-resistant transparency, etc.) is markedly lowered.

Further, in each of the alkali-developing resists typified by the color filter resist, the alkali-soluble resin imparts coating film formability and developer solubility to the resist, and the resist becomes a resistant component. It is also referred to as a binder resin due to this function. Further, it is also a component that affects various properties such as hardenability, adhesion, heat resistance, dry resolubility, and heat resistance, and in many cases, the adhesive resin is studied as a solution.

As a method for solving the problem of the resist for a color filter as described above, a method of investigating the adhesive resin has been proposed in large numbers, and as one of them, it has been proposed to use a master which is widely known for its excellent durability, particularly heat resistance. A resin having a ring structure in a chain as a method of bonding a resin (for example, refer to Patent Document 1 and Patent Document 2). In particular, when the resin described in Patent Document 1 is used, a coloring agent excellent in curability, solvent solubility, developability, dispersibility, adhesion, and the like can be obtained, and it is considered to be effective in the above-mentioned problems.

As described above, the resin having a ring structure in the main chain is excellent in durability and heat resistance, and is used in various applications. As a method of obtaining such a resin, there is a method of obtaining such a resin by the following method: The polycondensation mechanism or the addition polymerization mechanism bonds the monomers having a ring structure, and the ring structure derived from the monomers is directly incorporated into the main chain. For example, examples of the resin having a ring structure in the main chain produced by the polycondensation mechanism include polycarbonate, polyimide, and polyphenylene sulfide. This resin is very high in heat resistance and is mainly used in engineering plastics. However, it is manufactured under very severe conditions such as high temperature, high pressure conditions or conditions for producing hydrochloric acid, so it is difficult to achieve physical property adjustment corresponding to the use. Or a multi-functional topic.

On the other hand, the addition polymerization mechanism is easy to adjust the molecular weight and can be copolymerized with various vinyl monomers under mild conditions, so that it is easy to impart various functions other than the physical property adjustment or heat resistance corresponding to the application. Therefore, the addition polymerization mechanism is used as a method of synthesizing a resin which tends to be a high level of optical materials or a resist material and which is used for various functions. The resin having a ring structure in the main chain obtained by such an addition polymerization mechanism may, for example, be a cycloolefin polymer synthesized by coordination polymerization of a cyclic olefin or substituted by N for maleic acid A maleimide-based polymer synthesized by radical polymerization of an imide.

On the other hand, as a method of synthesizing a resin having a ring structure in a main chain, there is a method in which a monomer having no ring structure is cyclized and polymerized while being subjected to addition polymerization. As such a method, for example, a method in which a 1,6-diene is polymerized by a radical polymerization mechanism to obtain a resin having a 5-membered or 6-membered ring structure in a main chain is known (for example, refer to Non-Patent Document 1 and Non-Patent Document 1 Patent Document 2 and Non-Patent Document 3). This method forms a ring structure at the time of polymerization, and thus provides a novel synthesis method different from the above-described polycondensation or addition polymerization method in which a monomer having a ring structure is previously adjusted and polymerized.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2006-161035

Patent Document 2: Japanese Patent Laid-Open Publication No. 2003-201316

Non-patent literature

Non-Patent Document 1: Takashi Tsuda and another person, "Polymer" (Netherlands), 1994, Vol. 35, pp. 3317-3328

Non-Patent Document 2: Rovert D. Thompson and two others, "Macromolecules" (USA), 1992, Vol. 25, pp. 6555-6459

Non-Patent Document 3: Michio Urushisaki and four others, "Macromolecules" (USA), 1999, Vol. 32, pp. 322-327

As described above, the resin having a ring structure in the main chain used in various compositions, the resin composition thereof, and the method for producing the resin have been studied, but there are problems, and there is still room for further research.

In other words, a radically curable resin composition using a radical polymerizable monomer having a tetrahydroindenyl group or a binder resin having a tetrahydroindenyl group in a side chain is excellent in curability (oxygen scavenging property) in air, and Adhesion and transparency are also good, but there is still room for improvement in heat resistance.

As a resin for dispersing a composition of a colored material, the resin described in Non-Patent Document 1 and Patent Document 1 tends to cause abnormality in polymerization during polymerization (molecular weight distribution is extremely wide) or gelation, and is stable in production. There are problems with quality management. Moreover, there is still room for improvement in terms of coexistence of dispersibility and other performance.

In addition, as the resin for the photosensitive resin composition, the adhesive resin and the coloring resist described in Patent Document 2 are excellent in heat resistance and plate-making property, but cannot sufficiently cope with the high concentration of the colored material. In order to cope with the high concentration of the colored material, the adhesive resin and the coloring resist described in Patent Document 1 have improved the dispersion stability and the plate-making property of the colored material, but there is still room for improvement, and when the adhesive resin is produced. It is easy to cause abnormal polymer quantification or gelation, and it has problems in manufacturing stability and quality management.

Further, in the method of cyclizing and polymerizing a monomer having no ring structure while undergoing addition polymerization, a structural unit derived from a 1,6-diene monomer which is not cyclized and polymerized may be generated. (hereinafter also referred to as "unclosed loop unit"), the double bond which is present in the unclosed unit becomes a base point, branches and crosslinks, and causes abnormality of high molecular weight (molecular weight distribution becomes very wide) or gelation. Such a tendency is particularly strong under industrially and economically favorable conditions, such as conditions for increasing the conversion ratio of the monomer, conditions for increasing the polymerization concentration, and the like, and having a main chain of 1,6-diene monomer as a raw material. The industrialization of the resin of the ring structure has become a major obstacle.

The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a resin which can be suitably used in various applications such as a radical curable resin composition, a colored material dispersion composition, and a photosensitive resin composition, and a resin composition, and A method of making the resin.

In particular, it is an object of the invention to provide a binder resin for a radical-curable composition which is excellent in adhesion and transparency, and which is excellent in heat resistance, and a radical-curable composition using the binder resin.

Moreover, the present invention provides a resin for dispersing a coloring material which can coexist with dispersibility and other properties such as adhesion, hardenability, and the like, and a colored material dispersion composition using the resin.

Further, the present invention provides a novel alkali-soluble resin having a ring structure in a main chain having high heat resistance, excellent dispersion stability of a colored material, and excellent plate-making property, and a photosensitive resin composition using the resin as a binder resin. Things. Moreover, the present invention provides a color filter formed using the photosensitive resin composition, and a liquid crystal display panel including the color filter.

The present inventors conducted intensive studies on a polymer having a structural unit represented by the following formula (1) in the main chain. As a result, it has been found that a structure having a tetrahydrofuran ring (THF ring) in the main chain exhibits hardenability (oxygen scavenging property) in air, good adhesion, transparency, and excellent heat resistance, so that it can be suitably used in various applications. A radical curable resin composition used. Further, it has been found that the polymer is excellent not only in dispersibility of a colored material but also in adhesion and hardenability, and it has been found to be suitable for use in a highly functional colored material dispersion composition for use in various inks, paints and the like. Further, it has been found that the polymer is excellent not only in heat resistance and dispersibility of a colored material but also in plate-making property, and it has been found to be suitable for use in a photosensitive resin composition.

Further, the present inventors conducted various studies on a method of producing a polymer having a ring structure in a main chain by subjecting a 1,6-diene monomer to cyclization polymerization, and as a result, it has been found that a chain transfer which is usually used for adjusting molecular weight is obtained. The agent exerts a specific effect of inhibiting branching of the polymer in the cyclization polymerization of the specific 1,6-diene. That is, it has been found that since crosslinking can be suppressed by inhibiting branching, the chain transfer agent functions as a so-called anti-crosslinking agent, and the molecular weight distribution of the obtained polymer can be narrowed, or industrially and economically advantageous conditions. The gelation was not carried out to obtain a polymer. The chain transfer agent not only adjusts the molecular weight at the time of polymerization by chain transfer, but also has an effect of suppressing branching or preventing cross-linking and gelation accompanying the branch, which is not known.

That is, the above-described action and effect are phenomena which are exhibited when a specific 1,6-diene monomer is polymerized, and the purpose thereof is different from the use of a chain transfer agent which is generally used for adjusting the molecular weight, and is a new finding discovered by the present inventors.

Further, by suppressing branching, the heat resistance of the obtained polymer can be improved. Thus, it has been found that by using the production method of the present invention, the branching of the polymer can be prevented even in industrially advantageous conditions, for example, conditions in which the conversion rate is high or in the polymerization using a high concentration of the monomer component. A polymer having a ring structure and more excellent heat resistance.

That is, the present invention is an α-allyloxy methacrylic copolymer having a structural unit represented by the following formula (1) in the main chain.

(In the formula, R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms).

Further, the present invention is also a resin composition comprising the α-allyloxy methacrylic acid copolymer of the present invention and used for use in a photosensitive application, a dispersible use of a colored material, and a radical curable application. At least one use of the group of constituents.

Further, the present invention is also a process for producing an α-allyloxy methacrylic copolymer which is used for producing an α-allyloxy group having a structural unit represented by the following formula (1) in a main chain. Methacrylic copolymer:

(wherein R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms); and the above production method comprises a single one containing an α-allyloxymethylacrylic monomer represented by the following formula (2) The step of polymerizing the body components,

(In the formula, R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms).

The invention is described in detail below.

The α-allyloxy methacrylic acid copolymer of the present invention has a copolymer having a structural unit represented by the formula (1) in the main chain (in the present specification, it is sometimes referred to as "AMA copolymer (b)" When such a copolymer is used as a resin having a ring structure in a main chain to form a resin composition, a resin composition which can be suitably used for various purposes is formed.

Further, R in the formula (1) is the same as R in the formula (2) described later.

The α-allyloxy methacrylic acid copolymer is preferably obtained by a production method including a step of polymerizing a monomer component containing a monomer represented by the following formula (2).

(In the formula, R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms).

The a-allyloxymethylacrylic monomer (which may be referred to as "AMA monomer (a)" in the present specification) represented by the above formula (2) may be used alone or in combination of two or more. Further, the monomer component includes an AMA monomer (a) and another radical polymerizable monomer.

The above AMA monomer (a) will be described in detail.

The AMA monomer (a) is polymerized to form a structural unit represented by the above formula (1) at a high ratio, so that branching of the polymer is less likely to occur as compared with other 1,6-diene monomers. Therefore, it is difficult to cause abnormal polymerization or gelation.

R in the formula (2) which represents the structure of the above AMA monomer (a) is a hydrogen atom or an organic group having 1 to 30 carbon atoms. In the method for producing an α-allyloxymethyl acrylate copolymer of the present invention to be described later, the effect of suppressing branching of the polymer when a chain transfer agent is used is considered to be an olefin of the AMA monomer (a). This is caused by the dipropyl ether group, so even if the R changes, this effect is fully exerted. Further, each of the properties of the obtained α-allyloxymethyl methacrylate copolymer is represented by the structural unit represented by the above formula (1), the THF ring in the main chain and the methylene group located on both sides of the THF ring. Since R is caused, R may be appropriately selected depending on the purpose or use.

Further, as described above, if R in the formula (2) is a hydrogen atom or an organic group having 1 to 30 carbon atoms, no problem occurs, and it is generally considered that the groups do not interfere with the copolymer or the resin composition. The implementation of the methods of the present invention exerts the effects of the present invention.

Specific examples of the organic group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyloctyl group, a 2-ethylhexyl group, a lauryl group, and a stearyl group. a chain-like saturated hydrocarbon group; a methoxyethyl group, a methoxyethoxyethyl group, or the like, an alkoxy group substituted with a part of a hydrogen atom of a chain saturated hydrocarbon group; a propyl group, a hydroxybutyl group or the like substituted with a hydroxyl group to replace a part of a hydrogen atom of a chain saturated hydrocarbon group; a fluoroethyl group, a difluoroethyl group, a chloroethyl group, a dichloroethyl group, a bromoethyl group, a halogen-substituted chain-like saturated hydrocarbon group in which a halogen atom replaces a part of a hydrogen atom of a chain-like saturated hydrocarbon group; a chain-like unsaturated hydrocarbon group such as a vinyl group, an allyl group, a methallyl group, a butenyl group or a propynyl group; And a chain-unsaturated hydrocarbon group substituted with a part of hydrogen atoms thereof by an alkoxy group, a hydroxyl group or a halogen; a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 4-tert-butylcyclohexyl group, a tricyclodecyl group An alicyclic hydrocarbon group such as an isobornyl group, an adamantyl group or a dicyclopentadienyl group, and an alkoxy group An alicyclic hydrocarbon group in which a hydroxyl group or a halogen is substituted with a part of hydrogen atoms; an aromatic hydrocarbon group such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a 4-tert-butylphenyl group or a benzyl group; And an aromatic hydrocarbon group in which a part of hydrogen atoms are substituted with an alkoxy group, a hydroxyl group or a halogen; and if it is such an organic group (organic residue), it can be suitably used. Further, the organic groups may further bond the substituents. R of the AMA monomer (a) contained in the monomer component may be the same or two or more different types. That is, a structural unit derived from a plurality of AMA monomers (a) having different R may be contained in the AMA copolymer (b).

As described above, R in the above formula (2) is a hydrogen atom, a chain-like saturated hydrocarbon group, an alkoxy-substituted chain-like saturated hydrocarbon group, a hydroxy-substituted chain-like saturated hydrocarbon group, a halogen-substituted chain-like saturated hydrocarbon group, a chain-like unsaturated hydrocarbon group, Alkoxy-substituted chain unsaturated hydrocarbon group, hydroxy-substituted chain unsaturated hydrocarbon group, halogen-substituted chain unsaturated hydrocarbon group, alicyclic hydrocarbon group, alkoxy-substituted alicyclic hydrocarbon group, hydroxy-substituted alicyclic hydrocarbon group, halogen-substituted fat A cyclic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy-substituted aromatic hydrocarbon group, a hydroxy-substituted aromatic hydrocarbon group or a halogen-substituted aromatic hydrocarbon group is also one of suitable embodiments of the present invention.

Next, the AMA copolymer (b) obtained by radically polymerizing the monomer component containing the AMA monomer (a) will be described in detail.

The AMA copolymer (b) contains a structural unit represented by the above formula (1) in the main chain, and has a structure having a ring structure in the main chain, so that heat resistance is high. In general, a resin having a ring structure in the main chain has almost no flexibility even though it has high heat resistance, but a repeating unit having a THF ring represented by the above formula (1) has a methylene group on both sides of the THF ring. Therefore, the softness is also excellent. In the above AMA copolymer (b), R in the formula (1) may be different or may be the same in each structural unit.

Further, it is known that a tetrahydroindenyl group having a functional group of a THF ring captures oxygen by a mechanism represented by the following formula (3).

It is presumed that the α-allyloxymethyl acrylate copolymer of the present invention also exhibits oxygen scavenging performance as shown by the following formula (4).

(R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms). For example, when the AMA copolymer (b) is used in a radical curable resin composition or the like, it is generally considered to exhibit the following effects, that is, to reduce the use. The inhibition of free radical hardening by oxygen in the free radical hardening of heat or active energy rays. From this point of view, the AMA copolymer (b) of the present invention can be suitably used for a radical curable resin composition, and can improve surface hardenability and film hardenability. Further, since it has oxygen trapping properties, it can be suitably used as an oxygen absorbing film or a protective material for an organic electroluminescence device.

The above THF ring functions as a so-called Lewis base (donor of a lone pair). Therefore, for example, when the resin composition using the AMA copolymer (b) is bonded to another member, the THF ring easily interacts with the functional groups on the surface of the other member, and exhibits good adhesion. From this point of view, it can be suitably used for various resin compositions used in close contact with a substrate or the like.

The above AMA copolymer (b) has excellent transparency because the THF ring does not contain nitrogen (N). Thereby, it can be suitably used as an optical material such as a lens or a color filter.

The above AMA copolymer (b) has excellent dispersion stability of colored materials. It is generally believed that the reason is that the THF ring carried by the Lewis base interacts with the surface of the colored material (pigment, dye) or the functional group of the dispersing agent of the colored material. Therefore, the AMA copolymer (b) obtained by the production method of the present invention is suitably used for the use of a coloring material (pigment, dye) as a coating component, a coloring ink, a coloring resist, or the like. From this point of view, the AMA copolymer (b) of the present invention can be suitably used for a colored material dispersion composition.

In the colored material dispersion composition, when the AMA copolymer (b) has a high molecular weight, even if the content ratio of the structural unit represented by the formula (i) is small, the performance (the excellent dispersibility of the colored material) tends to be exhibited. When it is a low molecular weight, the increase in content tends to easily exhibit performance. The reason for this is considered to be related to the number of structural units represented by the formula (1) contained in each main chain (hereinafter referred to as "average functional group number"). From this point of view, the average functional group number is preferably 0.5 or more, more preferably 1.0 or more, still more preferably 2.0 or more. Further, the average number of functional groups is represented by the following formula.

Average functional group number = A/P

A: Molar number of the structural unit represented by the formula (1) contained in the unit mass [mol/g]

P: Moir number of the AMA copolymer (b) per unit mass [mol/g] If there are two or more types of structural units represented by the formula (1), A may be as follows Calculate.

A=ΣAX (X=1, 2, 3, ...)

AX = unit mass × (CX / 100) / FX

AX: Molar number of the structural unit represented by the formula (1) in the X (X = 1, 2, 3, ...) unit mass [mol/g]

CX: mass ratio of the structural unit represented by the formula (1) of the X (X = 1, 2, 3, ...) contained in the unit mass [% by mass]

FX: molecular weight [g/mol] of the structural unit represented by the formula (1) of X (X = 1, 2, 3, ...)

The number average molecular weight (Mn) of P using the AMA copolymer (b) can be approximated as follows.

P = unit mass / Mn

Mn: number average molecular weight of AMA copolymer (b)

Therefore, the average functional group number is represented by the following formula using CX, FX, and Mn.

Average functional group number = Mn × Σ {(CX/100) × (1/FX)}

(X=1, 2, 3, ...)

Further, in the 1,6-diene, the cyclization ratio of the AMA monomer (a) represented by the formula (2) (the structural unit represented by the formula (1) is formed from the monomer represented by the formula (2) The ratio is higher, so CX and FX can be approximated as follows.

CX: mass ratio of the AMA monomer (a) represented by the formula (2) of the reaction formula (2) to all monomers of the reaction [% by mass]

FX: molecular weight [g/mol] of the AMA monomer (a) represented by the formula (2) (X = 1, 2, 3, ...)

Further, when the reaction rate (conversion ratio) of each monomer used in the polymerization is high (for example, the reaction rate is 90 mol% or more), CX can be approximated as follows.

CX: the mass ratio [% by mass] of the AMA monomer (a) represented by the formula (2) (X = 1, 2, 3, ...) in the monomer component

Further, the above Mn can be measured by the measurement method used in the examples described later.

The above AMA copolymer (b) has excellent compatibility and dry resolubility. It is believed that this compatibility, dry resolubility is caused by the THF ring structure and the methylene group on both sides of the THF ring structure. It is also presumed that the tetrahydrofuran is excellent as a solvent having an ability to dissolve a very wide range of substances, and is preferably used for industrial use as well as for analysis or research.

As described above, the AMA copolymer (b) has various excellent properties and can be suitably used for various purposes. The properties caused by the above THF ring, for example, in a (meth)acrylic copolymer having a tetrahydroindenyl group on the side chain like a tetrahydrofurfuryl (meth) acrylate copolymer, can be exhibited, but it is difficult The α-allyloxymethylacrylic copolymer of the present invention exhibits high heat resistance or durability as usual. For example, when the AMA copolymer (b) is used for a curable resin composition, it can be suitably used for a sealing material or an overcoat layer for electronic parts, and since oxygen trapping property and high heat resistance can coexist, Therefore, it is possible to protect components and the like without being deteriorated by oxidation or heat.

The AMA copolymer (b) is an α-allyloxy methacrylic copolymer obtained by polymerizing an AMA monomer (a) with another radical polymerizable monomer, and accordingly, by using an AMA monomer (a) In addition to the excellent properties obtained, properties imparted by other polymerizable monomers can be imparted, and the properties of the obtained α-allyloxy methacrylic copolymer can be adjusted depending on the use or the like to be used.

The type of the other radical polymerizable monomer and the structure of the structural unit derived from another radical polymerizable monomer are not particularly limited. Further, the form thereof is not particularly limited, and examples thereof include any of a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer. In addition, the other radical polymerizable monomer means a radical polymerizable monomer other than the AMA monomer (a) which can be copolymerized with the AMA monomer (a). Other radical polymerizable monomers may be used alone or in combination of two or more.

The other radically polymerizable single system includes a monomer having a radical polymerizable unsaturated group which is polymerized by irradiation with heat or an active energy ray, or the like, a type, a usage amount, a molecular weight, and the like of the other radical polymerizable monomer. It suffices to select as appropriate according to the purpose and use.

The other radically polymerizable monomer may, for example, be a monofunctional radical polymerizable monomer. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, butyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylic acid 2-ethylhexyl ester, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate (meth)acrylates such as esters and glycidyl (meth)acrylate; N,N-dimethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, etc. (methyl Acrylamides; unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, vinylbenzoic acid; maleic acid, fumaric acid, itaconic acid, methyl cis-butane Unsaturated polycarboxylic acids such as enedioic acid and methyl fumaric acid; unsaturated anhydrides such as maleic anhydride and itaconic anhydride; styrene, α-methylstyrene, vinyltoluene, methoxy Aromatic vinyl such as styrene; methyl maleimide, ethyl maleimide, isopropyl maleimide, cyclohexyl maleimide, benzene Butylene (PEI), acyl benzyl maleic imide, maleic naphthyl acyl imine acyl N-substituted maleic imide and the like.

The weight average molecular weight (Mw) of the AMA copolymer (b) may be appropriately set according to the purpose and use, and is preferably used for liquid use such as a radical curable resin composition or a colored material dispersion composition. The fluidity is preferably 100,000 or less, more preferably 70,000 or less, and still more preferably 50,000 or less. Moreover, in order to fully exhibit the characteristics as a polymer, it is preferably 1,000 or more, and more preferably 3,000 or more.

The polydispersity (Mw/Mn) of the molecular weight distribution of the AMA copolymer (b) is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less. The production method of the present invention can suppress the branching of the polymer, so that Mw/Mn can be reduced.

In addition, the method of measuring the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) is not particularly limited, and for example, the measurement method used in the examples described later can be used.

Further, as a method for controlling the molecular weight of the AMA copolymer (b), a usual method can be used, and for example, it can be controlled by adjusting the amount or type of the polymerization initiator, the polymerization temperature, and the type or amount of the chain transfer agent. .

The AMA copolymer (b) of the present invention can impart properties such as oxygen trapping property, adhesion, discoloration of colored materials, compatibility, dry resolubility, transparency, and the like by a THF ring and methylene groups on both sides thereof. It is widely used in heat resistance and durability, so it can be widely used in adhesives, adhesives, dental materials, optical components, information recording materials, materials for optical fibers, color filter resistors, solder resists, and plating resistors. Agent, insulator, sealant, inkjet ink, printing ink, coating, injection molding material, decorative board, WPC (Wood-Plastic Composites), coating agent, photosensitive resin board, dry film, lining agent , civil construction materials, putty, maintenance materials, flooring materials, paving materials, gel coatings, outer coatings, hand coating / spray cloth, draw forming / filament winding / SMC (Surface Mount Component) Use of a molding material such as /BMC (Bulk Molding Compound) or a polymer solid electrolyte.

Next, the alkali-soluble resin of the present invention will be described.

The alkali-soluble resin of the present invention is characterized in that it has a structural unit represented by the above formula (1) in the main chain.

The content of the structural unit represented by the formula (1) of the alkali-soluble resin of the present invention may be appropriately set according to the purpose, the use, or the molecular weight of the alkali-soluble resin of the present invention, and is usually from 1 to 99 mol in all the repeating structural units. % is preferably from 2 to 98 mol%, more preferably from 5 to 95 mol%. When the alkali-soluble resin of the present invention has a high molecular weight, even if the content of the structural unit represented by the formula (1) is small, the performance tends to be exhibited, and when it is a low molecular weight, the increased content tends to exhibit performance. The reason for this is considered to be related to the number of structural units represented by the formula (1) contained in each main chain (hereinafter referred to as the average number of functional groups), and the average number of functional groups is preferably 0.5 or more. Preferably, it is 1.0 or more, and more preferably 2.0 or more.

Further, the average number of functional groups can be determined in the same manner as described above.

The alkali-soluble resin of the present invention has an acid group for achieving alkali solubility. The acid value of the alkali-soluble resin of the present invention is preferably a value of preferably from 10 to 300 mgKOH/g, more preferably from 15 to 250 mgKOH/g, still more preferably from 20 to 200 mgKOH/g, depending on the purpose or use. g. When the acid value of the alkali-soluble resin is in the above range, sufficient alkali solubility is exhibited, and in particular, when it is used for an alkali development type resist, good plate-making properties can be exhibited. When the alkali-soluble resin of the present invention has a high molecular weight, a high acid value can obtain a good plate-making property, and when it is a low molecular weight, a good plate-making property tends to be obtained even if the acid value is low.

Examples of the acid group for achieving alkali solubility include a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, a sulfonic acid group, and the like which can be neutralized with an alkali water, and may have only such a functional group. One type may have two or more types. Among these, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxyl group is preferable. The method of introducing an acid group includes a method of introducing a monomer component containing a monomer represented by the above formula (2) and a monomer having an acid group, or a method of introducing the above-mentioned formula in the main chain. (1) The resin of the structural unit shown is subjected to a two-stage or more introduction method of the upgrading treatment.

The monomer having an acid group in the above-described one-stage introduction method is a functional group having a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, a sulfonic acid group, etc., and a neutralization reaction with an alkali water, and a polymerizable unsaturated group. Base compound. Specific examples thereof include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; maleic acid, fumaric acid, itaconic acid, and methyl group. Unsaturated polycarboxylic acids such as maleic acid and methyl fumaric acid; mono(2-propenyloxyethyl) succinate, mono(2-methylpropenyloxyethyl) succinate An unsaturated monocarboxylic acid having a chain extending between an unsaturated group such as an ester and a carboxyl group; an unsaturated acid anhydride such as maleic anhydride or itaconic anhydride; and a phosphoric acid group such as Lightester P-7M (manufactured by Kyoeisha Chemical Co., Ltd.) In terms of versatility, availability, and the like, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, and unsaturated acid anhydrides) are preferred.

The method of introducing the two or more stages is not particularly limited as long as it does not lose the structural unit represented by the above formula (1) in the reforming treatment, and for example, a single one having a functional group p will be mentioned. After the polymerization of the monomer component of the bulk, a two-stage introduction method of reacting a compound having a functional group q capable of reacting with the functional group p to form an acid group is carried out. Further, after the monomer having the functional group r is polymerized, the functional group r may be converted into the functional group p by only the necessary number of times, and then the compound having the functional group q may be reacted in three stages or more. Import method. Examples of such a functional group p include an active hydrogen group such as a hydroxyl group or an amine group, and examples of the functional group q include a polybasic acid anhydride group.

Specific examples of the compound having the above polybasic acid anhydride group include succinic anhydride, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydrophthalic anhydride, and A. Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyl endomethylenetetrahydroortylene Formic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc., one or two of these may be used. More than one species.

As a two-stage introduction method in which a monomer component containing a monomer having a functional group p is polymerized and a compound having a functional group q capable of reacting with a functional group p to form an acid group is reacted, for example, A method in which a monomer component of 2-hydroxyethyl methacrylate is polymerized to react succinic anhydride. Further, as a method of introducing the above-described monomer having a functional group r, the reforming process is carried out only as many times as necessary to convert the functional group r into a functional group p, and then the compound having the functional group q is reacted. For example, a method of polymerizing a monomer component containing glycidyl (meth)acrylate, reacting (meth)acrylic acid, and further reacting succinic anhydride can be mentioned.

Next, a polymer having an acid group and having a radical polymerizable unsaturated group will be described.

The alkali-soluble resin of the present invention more preferably has a radical polymerizable unsaturated group. The content of the radically polymerizable unsaturated group may be appropriately set according to the purpose or use, and in order to obtain good plate-making property, a radical polymerizable unsaturated bond equivalent (radical polymerizable unsaturated bond per 1 chemical equivalent) The molecular weight) is preferably from 200 to 5,000, more preferably from 250 to 4,000, still more preferably from 300 to 3,000.

Examples of the radically polymerizable unsaturated group include an acrylonitrile group, a methacryl group, a vinyl group, an allyl group, and a methallyl group, and may have only one of these types, or may have two types. the above. Among these, from the viewpoint of reactivity, it is preferably an acrylonitrile group or a methacryl group. The method of introducing a radically polymerizable unsaturated group is a two-stage or more introduction method in which a reforming treatment is carried out after obtaining a resin having a structural unit represented by the formula (1) in the main chain.

The method of introducing the two or more stages is not particularly limited as long as it does not lose the structural unit represented by the above formula (1) in the reforming treatment, and for example, a monomer having a functional group s will be mentioned. After the polymerization of the monomer component, a two-stage introduction method of reacting a monomer having a functional group t reactive with a functional group s is carried out. Further, after the monomer having the functional group u is polymerized, the functional group u may be converted into the functional group s by only the necessary number of times, and then the monomer having the functional group t may be reacted in three stages or more. Import method.

Examples of the combination of such a functional group s and t include a carboxyl group and a hydroxyl group, a carboxyl group and an epoxy group, a carboxyl group and an oxetanyl group, a carboxyl group and an isocyanate group, a hydroxyl group and an isocyanate group, an acid anhydride group and a hydroxyl group, and an acid anhydride group. With an amine group and the like. Among these, a combination of a carboxyl group and an epoxy group is preferred from the viewpoint of the degree of rapidity of the modification treatment, heat resistance, and transparency.

Specific examples of the monomer having the above carboxyl group include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; maleic acid and antibutene; Unsaturated polycarboxylic acids such as acid, itaconic acid, methyl maleic acid, methyl fumaric acid; succinic acid mono(2-propenyloxyethyl) ester, succinic acid single (2-A) The unsaturated monocarboxylic acid which is extended by a chain between an unsaturated group and a carboxyl group, such as a propylene methoxyethyl ethyl ester, may be used alone or in combination of two or more.

Specific examples of the monomer having the above epoxy group include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, and β-ethyl shrinkage of (meth)acrylate. Glyceryl ester, vinylbenzyl glycidyl ether, allyl glycidyl ether, (meth)acrylic acid (3,4-epoxycyclohexyl) methyl ester, vinyl epoxy cyclohexane, etc., which can be used only One type or two or more types are used.

The two-stage introduction method of reacting a monomer component containing a monomer having a functional group s and reacting a monomer having a functional group t reactive with a functional group s, specifically, for example, includes A method in which a monomer component of glycidyl (meth)acrylate is polymerized to react (meth)acrylic acid. Further, after the monomer having the functional group u is polymerized, the functional group u is converted into the functional group s by only the necessary number of times, and then the monomer having the functional group t is reacted. Specific examples of the method include a method in which a monomer component containing 2-hydroxyethyl (meth)acrylate is polymerized, and then succinic anhydride is reacted to further react glycidyl (meth)acrylate.

The alkali-soluble resin of the present invention is a resin having an acid group. When a radically polymerizable unsaturated bond is introduced, it is necessary to introduce an acid group by some methods, using a carboxyl group as a functional group s and an epoxy group as a functional group. When t is used, when the carboxyl group is reacted with an epoxy group, the amount of the carboxyl group is excessively larger than the amount of the epoxy group, or the carboxyl group is reacted with the epoxy group to react the polybasic acid anhydride, whereby an acid group and a radical polymerizable property can be formed. Resin resin. Further, when an epoxy group is used as the functional group s and a carboxyl group is used as the functional group t, the polyvalent acid anhydride may be reacted by reacting a carboxyl group with an epoxy group.

When a carboxyl group is used as the functional group s and an epoxy group is used as the functional group t, specifically, for example, a method in which a monomer component containing (meth)acrylic acid is polymerized and glycidyl (meth)acrylate is used is used. In the ester reaction, the amount of the carboxyl group is made larger than the amount of glycidyl (meth)acrylate, or the succinic anhydride is further reacted by reacting glycidyl (meth)acrylate.

When an epoxy group is used as the functional group s and a carboxyl group is used as the functional group t, specifically, for example, a monomer component containing glycidyl (meth)acrylate is polymerized and then (methyl) is used. The acrylic acid reacts to react the succinic anhydride.

When a carboxyl group and an epoxy group are used as a combination of the functional groups s and t, the step of reacting the carboxyl group with the epoxy group is preferably at a temperature of 50 to 160 ° C in order to secure a good reaction rate and prevent gelation. The range is more preferably 70 to 140 ° C, more preferably 90 to 130 ° C.

In the step of reacting the carboxyl group with the epoxy group, in order to increase the reaction rate, a basic catalyst for esterification or transesterification and an acid catalyst which are generally used as a catalyst can be used, and the side reaction is small. In other words, it is preferably an alkaline catalyst. Further, among the basic catalysts, dimethylbenzylamine, triethylamine, tetramethylurea, and triphenylphosphine are preferred from the viewpoint of reactivity, workability, or halogen-free. These catalysts may be used singly or in combination of two or more. The amount of the catalyst to be used is preferably from 0.01 to 5.0% by mass, preferably from 0.1 to 3.0% by mass, based on the alkali-soluble resin of the present invention to which a radically polymerizable unsaturated bond is introduced.

In the step of reacting the carboxyl group with the epoxy group, in order to prevent gelation, it is preferred to carry out the addition of a polymerization inhibitor in the presence of a gas containing molecular oxygen. As the gas containing molecular oxygen, air or oxygen diluted with an inert gas such as nitrogen is usually used and blown into the reaction vessel. As the polymerization inhibitor, a polymerization inhibitor for a radical polymerizable monomer which is usually used can be used, and examples thereof include a phenolic inhibitor, an organic acid copper salt or phenothiazine. In the above, from the viewpoint of low coloration and polymerization inhibition ability, a phenol-based inhibitor is preferable, and among them, p-methoxyphenol and 6-t-butyl group are preferable in terms of availability and economy. 2,4-xylenol, 2,6-di-tert-butylphenol. These polymerization inhibitors may be used singly or in combination of two or more. The amount of use of the polymerization inhibitor is preferably in accordance with the present invention in which a radically polymerizable unsaturated bond is introduced from the viewpoint of ensuring a sufficient polymerization inhibitory effect and curability in forming a photosensitive resin composition. The alkali-soluble resin is used in an amount of 0.001 to 1.0% by mass, preferably 0.005 to 0.5% by mass.

The alkali-soluble resin of the present invention may have an epoxy group, and/or an oxetanyl group, and/or an alkoxyalkyl group. By having an epoxy group, and/or an oxetanyl group, and/or an alkoxyalkyl group, the crosslinking density can be increased in the thermal hardening step. When it has an epoxy group, and/or an oxetanyl group, and/or an alkoxyalkylene group, it can be suitably used as a resist for a color filter, especially for a photoresist for a photo spacer, and a protective film. A resin for a transparent resist or an interlayer insulating film with a resist.

The weight average molecular weight of the alkali-soluble resin of the present invention may be appropriately set according to the purpose and use, and is 2,000 to 250,000, preferably 3,000 to 200,000, more preferably 4,000 to 150,000, in order to obtain good plate-making properties.

Further, the weight average molecular weight can be, for example, a measurement method used in the examples described later.

Hereinafter, a method for producing the α-allyloxymethyl acrylate copolymer of the present invention will be described.

The method for producing an α-allyloxymethylacrylic copolymer of the present invention is a method for producing an α-allyloxymethylacrylic copolymer by polymerizing a monomer component containing the AMA monomer (a). The AMA copolymer (b) can be produced by cyclization polymerization of the AMA monomer (a). The AMA copolymer (b) has a ring structure (THF ring) in the main chain, and thus has excellent heat resistance, and further has a methylene group on both sides of the THF ring, so that the flexibility is high, and compatibility or solvent dissolution occurs. Excellent sex.

The content of the AMA monomer (a) may be appropriately set according to the purpose, the use or the molecular weight of the AMA copolymer (b), and is preferably from 1 to 99 mol%, more preferably from 2 to 2, based on the molecular weight of the AMA copolymer (b). 98 mol%, and more preferably 5 to 95 mol%. By setting it as such a range, the AMA copolymer (b) can exhibit the outstanding characteristics by the structural unit shown by Formula (1). Further, the above structural unit is a repeating unit constituting a polymer, and contains a plurality of structural units in one polymer.

For the above AMA monomer (a), the radical polymerization is easier to carry out the cyclization polymerization than the ionic polymerization, and the radical polymerization is an industrially advantageous polymerization method, so the above production method preferably includes the monomer component. The step of free radical polymerization. Further, in the case where the content of the AMA monomer (a) is large or the polymerization concentration is extremely high, the polymer is likely to be branched or gelled, and the above-described production method preferably includes the monomer component in the chain transfer. The step of performing free radical polymerization in the presence of a solvent. Branching of the polymer can be more effectively inhibited by using a chain transfer agent. Crosslinking occurs when the branch is carried out, indicating that the degree of dispersion (Mw/Mn) of the molecular weight distribution becomes large. When the crosslinking is further carried out, a solvent swelling (gelation) which is insoluble in a solvent is formed. This phenomenon can be suppressed by suppressing the branch. Further, the branched portion of the AMA copolymer tends to have poor heat resistance, and the heat resistance can be improved by suppressing branching.

In general, the chain transfer agent is used to adjust the molecular weight, and when the AMA monomer (a) is polymerized, it also plays a role in inhibiting the branching of the polymer, so that the molecular weight distribution of the obtained polymer can be narrowed, or industrially. Under the economically favorable conditions, gelation does not occur to obtain a polymer. For example, when polymerization is carried out using only a polymerization initiator without using a chain transfer agent, the molecular weight distribution becomes large, and gelation may occur depending on the case. Further, the branched portion of the AMA copolymer is slightly inferior in heat resistance, and the heat resistance of the produced AMA copolymer is also improved by suppressing branching.

The reason why the above-mentioned chain transfer agent also exerts a crosslinking inhibition effect (an effect of suppressing branching) on the AMA monomer (a) in the 1,6-diene monomer is not clear, and it is presumed that the cause is One of the two double bonds of the AMA monomer (a) is an allyl ether group. It is considered that the branching of the polymer in the cyclization polymerization of the 1,6-diene monomer is caused by the formation of an unclosed unit as shown in the following formula (5).

(In the formula, R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms), and a double bond existing in the unclosed unit is branched at a base point to carry out crosslinking. Therefore, in order to prevent branching, at least either of the following must be achieved: the cyclization rate is increased to minimize the unclosed unit, or the double bond of the unclosed unit is prevented from being polymerized. In the method for producing an α-allyloxy methacrylic acid copolymer of the present invention, the allyl ether structure of the AMA monomer (a) and the chain transfer agent are combined by some mechanism to increase the cyclization rate. The possibility, but it is generally believed that the double bond (allyl ether group) of the unclosed unit is prevented from being polymerized mainly by a chain transfer agent.

In the polymerization in which the above chain transfer agent is not used, when a radical is generated in the double bond of the unclosed unit in the above polymerization step and reacts with a double bond of a monomer or other unclosed unit, the growth reaction may continue and branch. Branching occurs and cross-linking occurs. Further, when reacting with a radical generated in a growing terminal radical of a polymer or a double bond of another unclosed unit, the radical may be branched due to rebonding of the radical, and branching proceeds to cause crosslinking. When such cross-linking is further carried out, there is also a case where the abnormality of the high molecular weight or gelation eventually occurs.

On the other hand, when the above chain transfer agent is used, it is considered that a double bond from a non-closed ring unit loses a radical, and instead, a radical derived from a chain transfer agent is generated. If the radical derived from the chain transfer agent has sufficient polymerization initiation ability, the polymerization is not stopped, and if it is preferentially reacted with the monomer than the double bond of the unclosed unit, the polymerization is continued without crosslinking. This effect is an effect unique to the use of the AMA monomer (a) represented by the above formula (2). For example, when a 1,6-diene having an ester group at the 2-position and the 6-position is polymerized, a cyclization polymerization is carried out to mainly form a 6-membered ring (tetrahydropyran ring), and the following formula (6) is caused. ) the reaction shown to produce an unclosed unit,

(wherein R is the same or different and represents a hydrogen atom or an organic group having 1 to 30 carbon atoms), but the double bond in the unclosed unit easily reacts with a double bond of a monomer or other unclosed unit, particularly Industrially and economically favorable conditions (for example, conditions in which the polymerization concentration is high or the conversion rate is high) are likely to cause abnormal polymerization or gelation.

In the production method of the present invention, as in the reaction represented by the above formula (5), polymerization is carried out using the AMA monomer (a), and the double bond of the unclosed unit becomes an allyl ether group. Moreover, it is presumed that when a chain transfer agent is used, the radical generated in the allyl ether group preferentially reacts with the chain transfer agent to generate a radical derived from the chain transfer agent, and the radical derived from the chain transfer agent is sufficient. It has the ability to initiate polymerization and has the function of preferentially reacting with the monomer.

The amount of the chain transfer agent used may be, depending on the type of the chain transfer agent, the content of the AMA monomer (a) contained in the monomer component, the target molecular weight, the polymerization concentration, the amount of the initiator used in combination, the polymerization temperature, and the like. It is preferable to use 0.03% by mass or more based on 100% by mass of the monomer component. By using in such a range, the effect obtained by using a chain transfer agent can be fully exerted, and branching of a polymer can be suppressed more effectively. The amount of the chain transfer agent used is more preferably 0.05% by mass or more. Further, it is more preferably 0.1% by mass or more. The amount of use of the chain transfer agent is not particularly limited, and the effect of the present invention is further exerted. However, even if it is used in an amount of more than necessary, it is uneconomical and the odor is a problem. The content is set to 20% by mass or less based on 100% by mass of the monomer component.

The chain transfer agent may be a compound which is industrially used as a chain transfer agent in the polymerization of a radically polymerizable vinyl monomer. From the viewpoints of availability, prevention of crosslinking ability, and reduction in polymerization rate, it is preferably a mercaptocarboxylic acid, a mercaptocarboxylic acid ester, an alkyl mercaptan, a mercapto alcohol, an aromatic mercaptan, or the like. A compound having a mercapto group such as a mercaptoisocyanuric acid (also referred to as a "thiol-based compound" or a "thiol-based chain transfer agent"). That is, the above chain transfer agent is preferably a compound having a mercapto group.

Specific examples of the compound having a mercapto group include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, and 2-ethylhexyl 3-mercaptopropionate. , n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3- Mercaptocarboxylic acid esters such as mercaptopropionate, dipentaerythritol hexa(3-mercaptopropionate); alkyl thiol, tert-butyl mercaptan, n-dodecyl mercaptan, 1,2-didecylethane, etc. a mercaptan; a mercapto alcohol such as 2-mercaptoethanol or 4-mercapto-1-butanol; an aromatic mercaptan such as phenyl mercaptan, m-toluene mercaptan, p-toluene mercaptan or 2-naphthyl mercaptan; A mercaptan chain transfer agent such as anthracene isocyanurate such as [(3-mercaptopropoxy)-ethyl]isocyanurate.

As the chain transfer agent, a chain transfer agent other than the compound having a mercapto group may also be used. Examples of the chain transfer agent other than the compound having a mercapto group include disulfides such as 2-hydroxyethyl disulfide and tetraethylammonium disulfide disulfide; and benzyl diethyl dithiocarbamate. Examples include dithiocarbamates; monomeric dimers such as α-methylstyrene dimer; and halogenated alkanes such as carbon tetrabromide.

Further, the chain transfer agent may be used alone or in combination of two or more.

The method of adding the above-mentioned chain transfer agent is carried out in at least a part of the period during which the polymerization reaction is carried out (the AMA monomer (a) and the state in which the radical which can initiate polymerization is present), and the chain transfer agent is present as described above. There is no particular limitation on the method of addition. For example, a method of adding one time before the start of the polymerization, adding it once in the polymerization process, starting the addition at the same time as the start of the polymerization, and continuing to add until the end of the polymerization is exemplified. From the viewpoint of reducing the amount of the chain transfer agent used and maximizing the effect thereof, it is preferred to start the addition at the same time as the initiation of the polymerization and continue to add until the end of the polymerization.

When the monomer component is polymerized in the presence of the above chain transfer agent, the residue of the bond chain transfer agent (the group forming part of the chain transfer agent) is bonded to the terminal of the obtained polymer. The residue of the chain transfer agent is not bonded to all of the α-allyloxy methacrylic copolymer obtained by polymerization, but at least one polymer having a residue to which a chain transfer agent is bonded at the end is produced. Furthermore, in the case where a chain transfer agent is used, it can be detected by elemental analysis or spectroscopic method (NMR (nuclear magnetic resonance), IR (infrared), UV (Ultraviolet), etc.) It is judged by an element or a functional group peculiar to the residue of the chain transfer agent.

In the polymerization step, polymerization is carried out by setting the concentration (polymerization concentration) of the monomer component to 15% by mass or more, whereby the polymerization conversion ratio can be increased or the polymerization time can be shortened, which is industrially and economically preferable. Further, when a 1,6-diene monomer is subjected to a cyclopolymerization polymerization, when the polymerization concentration is increased, the polymer tends to be branched, but a specific one, 6-two is used in the use of a chain transfer agent. When the olefin (AMA monomer (a)) is cyclized, the branching of the polymer can be suppressed even if the polymerization concentration is increased. The polymerization concentration in the above polymerization step is more preferably 20% by mass or more, still more preferably 25% by mass or more, and particularly preferably 30% by mass or more. In addition, the polymerization concentration is a monomer when the total amount of the monomer component and the chain transfer agent used in the polymerization step, and other components (polymerization initiator, solvent, and the like) to be added as needed is 100% by mass. The concentration of the component is usually a small amount of the chain transfer agent or the polymerization initiator used in the polymerization step. Therefore, when the polymerization using a solvent is carried out, the concentration of the monomer component when the total amount of the monomer component and the solvent used in the polymerization step is 100% by mass is used as the polymerization concentration. In other words, the polymerization step is preferably carried out by adding 100% by mass of the total of the polymerization solvent and the monomer component to a concentration (polymerization concentration) of the monomer component of 15% by mass or more.

As the polymerization method of the monomer component, various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and precipitation polymerization can be used as long as the polymerization is carried out by a radical polymerization mechanism. These polymerization methods may be appropriately selected depending on the purpose and use, and are preferably solution polymerization from the viewpoint of industrial advantages and ease of structural adjustment such as molecular weight. When solution polymerization is used, the AMA monomer (a) is dissolved in a polymerization solvent to carry out polymerization.

When the above-described cyclization polymerization is carried out by solution polymerization, a solution in which a polymerizable monomer which is a raw material is once dissolved in a polymerization solvent may be used, or a polymerization property which is added as a raw material in a stepwise manner with respect to a polymerization solvent may be used. Monomer method. In the form of a stepwise addition of a polymerizable monomer to the polymerization solvent in the above-described cyclization polymerization, for example, a polymerizable monomer may be continuously added, or a polymerizable monomer may be intermittently added. The method of adding it as a chain transfer agent is also the same.

When the polymerization is carried out using the solution in which the polymerizable monomer is once dissolved in the polymerization solvent, the polymerization concentration is a polymerization solvent, a polymerizable monomer and a chain transfer agent added at once, and other additives added as needed. The mass percentage (% by mass) of the polymerizable monomer to be added at a time when the total mass of the components is 100% by mass. When the method of the stepwise addition is used, the polymerization concentration is a stepwise addition of the polymerizable monomer when the total amount of the total mass of the polymerization solvent and the polymerizable monomer to be added stepwise is 100% by mass. Total mass percentage (% by mass). In addition, the amount of the chain transfer agent and the polymerization initiator used in the polymerization step is usually a small amount, and for the sake of convenience, the total amount of the monomer component and the solvent used in the polymerization step is set to 100% by mass. The concentration of the monomer component may be used as the polymerization concentration.

When the monomer component is polymerized by a solution polymerization method, the type or amount of the solvent used for the polymerization is not particularly limited as long as it is inactive to the polymerization reaction, and can be used according to the polymerization mechanism. The polymerization conditions such as the type or amount of the monomer, the polymerization temperature, and the polymerization concentration, or the use of the α-allyloxymethyl methacrylate copolymer are appropriately set.

Examples of the polymerization solvent to be used include alcohols, glycols, cyclic ethers, glycol ethers, esters of glycol monoethers, alkyl esters, ketones, aromatic hydrocarbons, and aliphatic groups. Hydrocarbons, decylamines such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, water, and the like. These may be used singly or in combination of two or more.

The polymerization initiation method of the monomer component may be carried out by supplying energy necessary for initiation of polymerization to a monomer component by an energy source such as self-heating or electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.) or an electron beam. Further, it is preferred to use a radical polymerization initiator together, whereby the energy necessary for the initiation of polymerization can be greatly reduced, and the reaction control becomes easy.

The method for producing the above α-allyloxymethylacrylic copolymer preferably comprises a step of polymerizing a monomer component containing the AMA monomer (a) in the presence of a radical polymerization initiator. Further, in the case where the content of the AMA monomer (a) is large or the polymerization concentration is extremely high, the branching or gelation of the polymer is likely to occur, and it is more preferable to include the single sheet containing the AMA monomer (a). The step of polymerizing the body component in the presence of a chain transfer agent and a radical polymerization initiator.

Examples of the radical polymerization initiator include a polymerization initiator which generates a radical by heat or light, and a polymerization initiator which generates a radical by heat industrially and economically (thermal radical polymerization) The initiator is advantageous and preferred. The thermal radical polymerization initiator is not particularly limited as long as it generates a radical by supplying thermal energy, and may be appropriately selected depending on polymerization conditions such as a polymerization temperature, a solvent, and a type of the monomer to be polymerized.

The above-mentioned thermal radical polymerization initiator may, for example, be a peroxide or an azo compound, and these may be used singly or in combination of two or more. Further, a reducing agent such as a transition metal salt or an amine may be used in combination with the polymerization initiator.

The amount of the polymerization initiator to be used is not particularly limited as long as it is appropriately set depending on the type or amount of the monomer to be used, the polymerization temperature, the polymerization concentration, the molecular weight of the target polymer, and the like, and is not particularly limited. The polymer having a molecular weight of several thousands to several tens of thousands is preferably 0.05 to 20% by mass, and more preferably 0.1 to 15% by mass based on 100% by mass of all the monomer components.

The polymerization temperature or polymerization time which is preferable in the above cyclization polymerization varies depending on the type of the polymerizable monomer to be used, the use ratio, and the like, and is preferably 50 to 200 ° C, more preferably 70 to 150 ° C. The polymerization time is preferably 20 hours or shorter, more preferably 10 hours or shorter, and still more preferably 8 hours or shorter.

In order to obtain economical efficiency or to reduce the adverse effect of residual monomers on performance for various uses, it is preferred to carry out the conversion of the AMA monomer to 70% or more. That is, in the above polymerization step, the conversion ratio of the AMA monomer (a) is preferably 70% or more. In general, when the 1,6-diene is cyclized, if the conversion is increased, the branching of the polymer tends to occur, but the specific 1,6-diene (AMA single) is used in the chain transfer agent. In the case of the ring (a)) cyclization polymerization, the branching of the polymer can be suppressed even if the conversion rate is increased. The conversion ratio is more preferably 80% or more, still more preferably 85% or more, and particularly preferably 90% or more.

The method for producing the AMA copolymer (b) may further include a step of further modifying the monomer component containing the AMA monomer (a) represented by the formula (2). By performing the upgrading treatment, introduction of a radical polymerizable unsaturated group, introduction of a graft chain, or the like can be performed. In particular, when the AMA copolymer (b) having a radical polymerizable unsaturated group is formed by a modification treatment, for example, when the AMA copolymer (b) is used for a radically curable resin composition, the curability is The aspect of improvement is better. In other words, the AMA copolymer (b) may be obtained by polymerizing a monomer component containing the AMA monomer (a) represented by the formula (2) and then modifying the monomer component.

The method of the above-described modification treatment is not particularly limited as long as it does not lose the structural unit represented by the formula (1) in the AMA copolymer (b), and for example, a single one having a functional group x will be mentioned. A method of reacting a compound having a functional group y reactive with a functional group x after polymerization of a monomer component of the body.

Examples of the combination of the functional groups x and y include a carboxyl group and a hydroxyl group, a carboxyl group and an epoxy group, a carboxyl group and an isocyanate group, a hydroxyl group and an isocyanate group, an acid anhydride group and a hydroxyl group, an acid anhydride group, and an amine group. Specifically, for example, an AMA copolymer (b) having a radical polymerizable unsaturated group can be formed by reacting a monomer component containing (meth)acrylic acid and then reacting glycidyl (meth)acrylate. Further, the AMA copolymer (b) having a polycaprolactone on the graft chain can be obtained by polymerizing a monomer component containing glycidyl (meth)acrylate and then reacting the single-end carboxyl group polycaprolactone.

Further, the present invention is an α-allyloxymethylacrylic copolymer (AMA copolymer (b)) produced by the above production method.

The α-allyloxy methacrylic acid copolymer may be one obtained by polymerizing one AMA monomer (a) or a plurality of AMA monomers (a).

The method for producing an α-allyloxymethylacrylic polymer having a structural unit represented by the following formula (1) in such a main chain is also one of the inventions.

(wherein R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms); and the above production method comprises the step of forming an α-allyloxymethylacrylic monomer represented by the following formula (2) only Step of polymerizing monomer components,

(In the formula, R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms).

The resin composition of the present invention, that is, the radical curable resin composition, the colored material dispersion composition, and the photosensitive resin composition will be described in order.

The radically curable resin composition of the present invention comprises a radical polymerizable monomer and a binder resin, wherein the binder resin is a resin having a structural unit represented by the formula (1) in the main chain. Further, the binder resin used in the radically curable resin composition of the present invention, that is, the binder resin for the radically curable resin composition of the resin having the structural unit represented by the formula (1) in the main chain is also It is one of the inventions.

First, each constituent component of the radical curable resin composition of the present invention will be described.

The essential component of the radical curable resin composition of the present invention is (A) a radical polymerizable monomer and (B) a binder resin, and (B) the binder resin has a structural unit represented by the formula (1) in the main chain. Resin. The radically curable resin composition of the present invention preferably contains (C) a radical polymerization initiator for improving hardenability in addition to the above-mentioned essential components, and further, may be based on a radical polymerizable monomer or a binder resin. (D) thinner, (E) other ingredients, depending on the type, purpose of each use, or required characteristics. Hereinafter, each component constituting the radical curable resin composition of the present invention will be described.

(A) Radical polymerizable monomer

The radically polymerizable single system has a radically polymerizable unsaturated group-containing low molecular compound which is polymerized by irradiation with heat or an active energy ray, and imparts radical curability to the radically curable resin composition. In particular, a liquid having a low viscosity at normal temperature has a function as a diluent for viscosity adjustment, and is also referred to as a reactive diluent, and is particularly preferably used for the use of a solvent. As such a radically polymerizable monomer, a user which is generally used as a radical polymerizable monomer can be used, and one or two or more types may be appropriately selected depending on the purpose and use. The radical polymerizable monomer can be classified into a monofunctional radical polymerizable monomer having only one radical polymerizable unsaturated group in the same molecule, and a polyfunctional group having two or more radical polymerizable unsaturated groups. A free radical polymerizable monomer.

As the monofunctional radical polymerizable monomer, the same as the other radical polymerizable monomer shown in the above-mentioned α-allyloxymethylacrylic copolymer production method can be used.

Among the above polyfunctional radically polymerizable monomers, polyfunctional (meth)acrylates and polyfunctional (meth)acrylic acid amides can be preferably used in terms of reactivity, economy, availability, and the like. A polyfunctional monomer having a (meth) acrylonitrile group such as an ester or a (meth) acrylonitrile-containing isocyanurate.

The molecular weight of the radical polymerizable monomer may be appropriately set according to the purpose and use, and is preferably 2,000 or less in terms of handling.

The amount of the radical polymerizable monomer to be used may be appropriately set depending on the type, purpose, and use of the radical polymerizable monomer or the binder resin to be used, and the properties of the radical curing property and the binder resin are excellent. The viewpoint is 5 to 1000% by mass, preferably 15 to 700% by mass, and more preferably 20 to 500% by mass based on the binder resin.

(B) Adhesive resin

The binder resin is mainly a polymer compound which affects the coating property after drying or the physical properties of the coating film after curing, and is a component which contributes to the radical hardening property to a large extent. As the binder resin for the radical curable resin composition of the present invention, the above α-allyloxymethacrylic acid copolymer can be used. Such a resin can reduce the inhibition of oxygen radical polymerization, and is excellent in adhesion and transparency, and is excellent in heat resistance.

It is generally presumed that the above-described characteristics of the binder resin for the radical curable resin composition of the present invention are represented by the THF ring contained in the structural unit represented by the formula (1), and the argon ring on both sides of the THF ring. Caused by methyl. Further, as described above, the adhesive resin of the present invention also exhibits an effect of reducing the inhibition of oxygen on the radical hardening. Further, it is considered that the THF ring easily interacts with the functional groups on the surface of the substrate, so that it exhibits good adhesion.

As one of suitable use forms of the radical curable resin composition of the present invention, a colored material (pigment, dye) is added as a coating material, a colored ink, a coloring resist, etc. as a component to form a colored radical-curable resin. In the use of the material, the binder resin of the radical curable resin composition of the present invention has excellent dispersion stability of the colored material as described later. It is generally believed that the reason is that the THF ring carried by the Lewis base interacts with the surface of the colored material (pigment, dye) or the functional group of the dispersing agent of the colored material.

It is considered that the binder resin for a radical curable resin composition of the present invention effectively exhibits the above properties because of the structure of a methylene group on both sides of the THF ring in the structure. Regarding the properties due to the THF ring, the (meth)acrylic copolymer having a tetrahydroindenyl group in the side chain may also be expressed to some extent, but it is difficult to exhibit the radical curable resin of the present invention. The composition is highly heat resistant like a binder resin. One of suitable use forms of the radical curable resin composition of the present invention is a sealing material or an overcoat layer for electronic parts, because the radical curable resin composition of the present invention has oxygen scavenging Properties (ie, antioxidant capacity) and higher heat resistance protect elements and the like without deterioration due to oxidation or heat.

The weight average molecular weight of the binder resin for the radical curable resin composition of the present invention may be appropriately set according to the purpose and use, and is usually 2,000 to 250,000, preferably 3,000 to 200,000, and more preferably 4,000 to 150,000.

Further, the weight average molecular weight can be, for example, a measurement method used in the examples described later.

The ratio of the binder resin for the radically curable resin composition of the present invention in the radically curable resin composition of the present invention is appropriately set depending on the type, purpose, and use of the radical polymerizable monomer or binder resin to be used. That is, it is preferably used in an amount as shown by the above-mentioned radical polymerizable monomer.

Further, as described above, the binder resin for the radical curable resin composition may be the same as the α-allyloxymethyl acrylate copolymer as described above, or may be used only by the AMA alone. The α-allyloxymethylacrylic acid polymer obtained by polymerizing the monomer component of the body (a). In this case, the same effect as in the case of using an α-allyloxymethacrylic copolymer can also be expected. That is, the use of the above α-allyloxymethyl acrylate polymer as the binder resin for the radical curable resin composition is also one of the inventions.

(C) Free radical polymerization initiator

The method of curing the radical curable resin composition of the present invention is to supply a radical to the radical curable resin composition of the present invention from an energy source such as heat or electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.) or an electron beam. The energy necessary for the initiation of the polymerization may be sufficient. When the radical polymerization initiator is further used in combination, the energy necessary for the initiation of radical polymerization can be largely reduced, and the hardenability can be improved, which is preferable. As a radical polymerization initiator, there is a thermal radical polymerization initiator which generates a polymerization initiation radical by heating, and a light free radical which generates polymerization initiation radical by irradiation with an energy beam such as an electromagnetic wave or an electron beam As the base polymerization initiator, one type or two or more types which are usually used can be used. Further, it is also preferred to add one or two or more kinds of thermal radical polymerization accelerators, photosensitizers, photoradical polymerization accelerators and the like which are usually used.

The total amount of the radical polymerization initiator to be added is not particularly limited as long as it is appropriately set according to the purpose and use, and is a viewpoint of the balance between the curability, the adverse effect of the decomposition product, and the economy. The total amount of the radical curable resin composition is preferably from 0.01 to 30% by mass, more preferably from 0.05 to 20% by mass, even more preferably from 0.1 to 15% by mass.

The total amount of the above-mentioned thermal radical polymerization accelerator, the photosensitizer, and the photo-radical polymerization accelerator is not particularly limited as long as it is appropriately set according to the purpose and use, and the curability and the adverse effects of the decomposition product are From the viewpoint of the balance of the economy, the total amount of the radical curable resin composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.05 to 10% by mass.

(D) thinner

In the radically curable resin composition of the present invention, in order to reduce the viscosity, the handleability is improved, a coating film is formed by drying, a dispersion medium as a colored material, or the like, and may be added in addition to the above-mentioned essential components as needed. A low-viscosity organic solvent or water in which each component in the radical curable resin composition is dissolved or dispersed is used as a diluent.

As the above diluent, the same polymerization solvent as that shown in the above-mentioned α-allyloxy methacrylic copolymer production method can be used. These may be used singly or in combination of two or more.

The amount of the above-mentioned diluent is not particularly limited as long as it is appropriately set according to the purpose and use, and is usually preferably 0 to 90% by mass, more preferably 0 to 80, based on the total amount of the radically curable resin composition. quality%.

(E) Other ingredients

In the radically curable resin composition of the present invention, a filler, a resin other than the binder resin for a radical curable resin composition of the present invention, and a colored material (pigment, dye) may be blended according to the purpose of each use or required characteristics. , dispersant, plasticizer, polymerization inhibitor, ultraviolet absorber, antioxidant, matting agent, defoamer, leveling agent, antistatic agent, dispersant, smoothing agent, surface modifier, thixotropic agent, touch A component other than the above-mentioned essential components such as a coupling agent, a decane-based or a coupling agent such as an aluminum-based or titanium-based compound, a cationically polymerizable compound, or an acid generator.

For example, when the radical curable resin composition of the present invention is used for an adhesive or an adhesive, the free radical curable resin composition of the present invention may be viscous with a resin other than the adhesive resin, an adhesive or the like as needed. A further imparting agent, various fillers, a colored material, a dispersing agent, and the like. The use of the thus obtained adhesive or adhesive on metal, glass, paper, resin, other substrates, and hardening by heating or active energy ray irradiation is a suitable implementation of the present invention. One of the forms.

When the radical curable resin composition of the present invention is used for an ink or a coating application, a resin other than the binder resin, various fillers, a colored material, a dispersing agent, and the like may be added to the radical curable resin composition of the present invention as needed. Dry oil, desiccant, etc. Applying the ink or coating thus obtained to a metal, glass, paper, resin, or other substrate and hardening it by heating or active energy ray irradiation is a suitable embodiment of the present invention. One.

When the radical curable resin composition of the present invention is used for a curable molding material, the resin other than the binder resin for the radical curable resin composition of the present invention, various fillers, colored materials, and dispersing agents may be blended as needed. , UV absorbers, etc. The hardened molding material thus obtained is directly impregnated into a reinforcing fiber such as glass fiber, carbon fiber or aromatic polyamide fiber, and then hardened by heating or active energy ray irradiation. One of the suitable embodiments of the invention.

When the radical curable resin composition of the present invention is used for a resist application, an alkali-soluble adhesive resin, an epoxy resin, various fillers, a colored material, a dispersant, and the like may be blended as needed. The resist material obtained in this manner is applied to a metal, glass, resin, or other substrate, and is cured by irradiation with an active energy ray, and then developed by an alkaline developing solution to form an image. Is one of the suitable embodiments of the present invention.

The radically curable resin composition of the present invention can be obtained by blending, dissolving or dispersing a compound having a radical polymerizable monomer, a binder resin, and other additives.

The radical curable resin composition of the present invention can be widely used for an adhesive, an adhesive, a biological material, a dental material, an optical member, an information recording material, a material for an optical fiber, a color filter resist, a solder resist, and a plating. Resistors, insulators, sealing materials, inkjet inks, printing inks, coatings, injection molding materials, decorative panels, WPC, coated materials, photosensitive resin sheets, dry films, lining materials, civil construction materials, putty, maintenance materials, Floor materials, paving materials, gel coats, top coats, hand-coated/sprayed/drawing-formed/filament-wound/SMC/BMC molding materials, polymer solid electrolytes, etc.

Next, the colored material dispersion composition of the present invention will be described.

The colored material dispersion composition of the present invention comprises a colored material, a dispersing agent, a binder resin, and a liquid medium, wherein the binder resin is a resin having a structural unit represented by the formula (1) in the main chain. Further, the binder resin used in the dispersion composition of the colored material of the present invention, that is, the binder resin for the colored material dispersion composition of the resin having the structural unit represented by the formula (1) in the main chain, is also the invention. one.

First, each constituent component of the colored material dispersion composition of the present invention will be described. The essential components of the colored material dispersion composition of the present invention are (F) colored material, (G) dispersant, (H) binder resin, and (I) liquid medium, and (H) binder resin has the above formula in the main chain ( 1) Resin of the structural unit shown. Further, other components other than the above (J) may be further blended depending on the purpose of each use or the required characteristics.

Hereinafter, each component constituting the dispersion composition of the colored material of the present invention will be described.

(F) colored materials

The colored material is a coloring material dispersion composition of the present invention, and a dye or a pigment which is generally used as a colored material can be used, and from the viewpoint of durability, a pigment (organic pigment, inorganic pigment) is preferred.

The colored materials may be used alone or in combination of two or more. Further, those having an appropriate average particle diameter may be used depending on the purpose and use. For example, when transparency is required, a smaller average particle diameter of 0.1 μm or less is preferable; when concealing is required, a larger average particle diameter of 0.5 μm or more is preferable. Further, the above-mentioned colored material may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, cerium oxide coating, wax coating, etc., depending on the purpose and use.

The proportion of the colored material in the dispersion composition of the colored material of the present invention may be appropriately set according to the purpose and use, and is generally preferable in the dispersion of the colored material in terms of obtaining a balance between the coloring power and the dispersion stability. It is 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, still more preferably 1 to 50% by mass.

(G) dispersant

The dispersing agent has an interaction site with the colored material and an interaction site with the dispersion medium (liquid medium or adhesive resin), and has a function of stabilizing the dispersion of the colored material in the dispersion medium, and can be used as a dispersing agent. Dispersant. It is generally classified into a resin type dispersant (polymer dispersant), a surfactant (low molecular dispersant), and a dye derivative.

The above dispersing agents may be used alone or in combination of two or more. The ratio of the dispersing agent in the colored material dispersion composition of the present invention may be appropriately set according to the purpose and use, and in order to achieve dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) or transparency, The amount of the colored material is usually preferably from 0.01 to 60% by mass, more preferably from 0.1 to 50% by mass, even more preferably from 0.5 to 40% by mass.

(H) Adhesive resin

As the binder resin for the colored material dispersion composition of the present invention, the same as the binder resin for the radical curable resin composition of the present invention can be used. It is considered that the radically curable resin composition of the present invention has a THF ring in the structure with a binder resin, that is, the so-called Lewis base is not as strong as an amine as a strong base, and has a suitable base. It does not interfere with the action of the dispersant, but interacts with the colored material and the dispersant to make the colored material dispersed by the dispersant more stable.

The ratio of the binder resin for the colored material dispersion composition of the present invention in the dispersion composition of the colored material of the present invention may be appropriately set according to the purpose and use, and is usually preferably 0.1 to 90% by mass in the dispersion composition of the colored material. More preferably, it is 0.5 to 80% by mass, and more preferably 1 to 70% by mass.

(I) Liquid medium

The liquid medium uniformly disperses a dispersion medium of a colored material dispersed by a dispersant, and is mainly a liquid substance having an action of adjusting viscosity, coating characteristics, drying characteristics, and the like of the dispersion composition of the colored material. As such a liquid medium, a liquid medium which is usually used can be appropriately selected depending on the purpose and use.

The amount of the liquid medium to be used may be appropriately set according to the purpose and use, and is usually preferably from 10 to 95% by mass, more preferably from 20 to 90% by mass, even more preferably 30% by weight of the colored material dispersion composition. ~85 mass%.

(J) Other ingredients

The colored material dispersion composition of the present invention may further contain components other than the above-mentioned essential components in accordance with the purpose of each use or the required characteristics. For example, in the photocurable ink, it is preferred to prepare a photopolymerizable monomer or a photoinitiator in addition to the above-mentioned essential components. In the air-curable coating material, it is preferred to prepare a dryness such as linseed oil in addition to the above-mentioned essential components. Desiccant such as oil or cobalt octoate.

In an alkali-developing resist ink such as a solder resist or a color filter resist, it is preferred to mix an alkali-soluble adhesive resin, an epoxy resin, and a radical curable unsaturated group in addition to the above-mentioned essential components. Resins, multifunctional acrylates, and photoinitiators.

Further, a stabilizer such as an antioxidant or an ultraviolet absorber, a leveling agent, a coupling agent such as decane or aluminum or titanium may be blended as needed.

The colored material dispersion composition of the present invention can be produced by a usual dispersion method, and may be appropriately selected depending on the purpose and use. Examples of the dispersing machine that can be used include a paint regulator, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, a blender, and the like. When the colored material is made into a small particle size, it is preferably subjected to kneading and dispersion treatment by a roll mill, a kneader, a blender or the like, and then subjected to a micro-dispersion treatment using a media mill such as a bead mill, and further preferably The fine waste is removed by filtering by a filter or the like as needed.

The method of adding the constituents of the dispersion to the dispersing machine may be added in a single order or sequentially, and the order may be arbitrary, and may be appropriately selected depending on the type of the dispersing machine or the like. Further, the constituent components (colored material, dispersant, binder resin, liquid medium, and other components) need not be added to the disperser, and the colored material and the minimum colored material necessary for dispersing the colored material by the disperser may be used. The components other than the colored material are further added and mixed, and the components other than the colored material are further added to and mixed with the dispersing agent to prepare a dispersion of the colored material containing the colored material at a high concentration.

Next, the photosensitive resin composition of the present invention will be described.

The photosensitive resin composition of the present invention contains an alkali-soluble resin having a structural unit represented by the above formula (1) in the main chain as a binder resin. Moreover, the present invention is also a color filter having a segment formed using the photosensitive resin composition, and a liquid crystal display panel including the color filter.

The photosensitive resin composition of the present invention contains (K) the alkali-soluble resin of the present invention, (L) a radically polymerizable monomer, (M) a photoinitiator, and (N) a solvent as essential components, and is excellent in that it is excellent. It is heat-resistant and is suitable for use as a resist for forming components in the field of electronic information, and is suitable for a resist for color filters. Further, since it has excellent dispersion stability of the colored material, the use of the (O) colored material as an essential component in addition to the above-mentioned essential components to form a photosensitive colored resin composition is the most effective use of the alkali-soluble resin of the present invention. One of the characteristic use forms, such a photosensitive colored resin composition is particularly suitable as a coloring resist for color filters. Further, (P) other components may be formulated according to each use or purpose.

Among the resists for color filters, there are colored resists (resistors for forming red, green, and blue pixels or black matrix), resists for optical spacers, transparent resists for protective films, and interlayer insulating films. A resist or the like is used corresponding to the resist constituting each portion of the color filter.

Hereinafter, the constituent components of the photosensitive resin composition of the present invention will be described based on the resist for a color filter of the present invention, but the present invention is not limited thereto.

(K) alkali-soluble resin of the present invention

The alkali-soluble resin of the present invention imparts coating film formability and alkali solubility to the resist, and also has a dispersion medium as the dispersed colored material when the photosensitive resin composition of the present invention is a photosensitive colored resin composition. Features.

The alkali-soluble resin of the present invention has excellent dispersibility of a colored material in addition to high heat resistance, and is excellent as a photosensitive colored resin composition, and is particularly suitable as a coloring resist for color filters. The coloring resist for a color filter is usually prepared by preparing a colored material dispersion (polishing slurry) composed of a colored material, a dispersing agent, a binder resin, a solvent, or the like, and further adding a radical polymerizable monomer, a photoinitiator, It is prepared by bonding a transparent resist liquid composed of a resin or a solvent. The alkali-soluble resin of the present invention is suitable as an adhesive resin for a polishing slurry, and is also suitable as a binder resin for a transparent resist liquid, and can be used for either or both of them. Further, it may be used by being mixed with an adhesive resin other than the alkali-soluble resin of the present invention. The preferred structure of the alkali-soluble resin of the present invention is as described above, and as a coloring resist, a structure having a radical polymerizable unsaturated group in a side chain is particularly preferable.

The alkali-soluble resin of the present invention has an effect of improving mechanical properties (recovery rate, etc.) or various plate-making properties in addition to high heat resistance, and therefore can be suitably used for a resist for a photo spacer. When the alkali-soluble resin of the present invention is used for a resist for a photo spacer, the structure is preferably as described above, and particularly preferably has a radical polymerizable unsaturated group, and/or an epoxy group, and/or a side chain. The structure of oxetanyl and/or alkoxyalkyl.

The alkali-soluble resin of the present invention is excellent in adhesion and transparency in addition to high heat resistance, and can be suitably used as a resist for a protective film or a resist for an interlayer insulating film. When the alkali-soluble resin of the present invention is used as a resist for a protective film or a resist for an interlayer insulating film, the structure is preferably as described above, particularly preferably having a radical polymerizable unsaturated group in a side chain, and/or The structure of an epoxy group, and/or an oxetanyl group, and/or an alkoxyalkyl group.

The ratio of the alkali-soluble resin of the present invention contained in the photosensitive resin composition of the present invention may be appropriately set according to the purpose and use, and among the components other than the solvent (N) in the photosensitive resin composition, usually It is preferably from 1 to 90% by mass, more preferably from 3 to 80% by mass, still more preferably from 5 to 70% by mass.

(L) radical polymerizable monomer

The radically polymerizable single system has a low molecular compound of a radical polymerizable unsaturated group which is polymerized by irradiation with an active energy ray such as an electromagnetic wave (infrared rays, ultraviolet rays, X-rays, or the like) or an electron beam, and is sensitized to the present invention. The resin composition imparts curability. As described above, the radical polymerizable monomer can be classified into a monofunctional radical polymerizable monomer having only one radical polymerizable unsaturated group in the same molecule, and having two or more radical polymerizable unsaturated groups. The polyfunctional radical polymerizable monomer is preferably a polyfunctional radical polymerizable monomer from the viewpoint of curability. As the radical polymerizable monomer, the same as the radical polymerizable monomer contained in the radical curable resin composition of the present invention described above can be used.

The molecular weight of the radical polymerizable monomer may be appropriately set according to the purpose and use, and is preferably 2,000 or less in terms of handling.

The amount of the radically polymerizable monomer to be used may be appropriately set depending on the type, purpose, and use of the radical polymerizable monomer or the binder resin to be used, and is formed of a self-photosensitive resin in order to obtain good plate-making properties. The component other than the solvent (N) is usually preferably from 3 to 90% by mass, more preferably from 5 to 80% by mass, even more preferably from 10 to 70% by mass.

(M) photoinitiator

The photosensitive resin composition of the present invention contains a photoinitiator which generates a polymerization initiation radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam, and one or two or more kinds of radical curability of the present invention can be used. The photoradical polymerization initiator represented by the component which the resin composition can contain is the same. Further, similarly to the photoradical polymerization initiator, one or two or more kinds of the photosensitizer, the photoradical polymerization accelerator, and the like are preferably added.

The total amount of the photoinitiator to be added is not particularly limited as long as it is appropriately set according to the purpose and use, and is self-photosensitive from the viewpoint of the balance between the curability, the adverse effect of the decomposition product, and the economy. The component other than the (N) solvent in the resin composition is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 25% by mass, still more preferably from 1 to 20% by mass.

The total amount of the photosensitizer and the photo-radical polymerization accelerator to be added is not particularly limited as long as it is appropriately set according to the purpose and use, and the balance between the curability, the adverse effect of the decomposition product, and the economy is considered. In the photosensitive resin composition, the component other than the (N) solvent is preferably 0.001 to 20% by mass, more preferably 0.05 to 15% by mass, still more preferably 0.01 to 10% by mass.

(N) solvent

The solvent is a low-viscosity organic solvent or water which can be used to form a coating film by drying, to form a coating film by drying, to be used as a dispersion medium of a colored material, and to dissolve or disperse each component in the photosensitive resin composition. .

As the solvent, the same diluent as the component which can be contained in the radical curable resin composition of the present invention can be used alone or in combination of two or more.

The amount of the solvent to be used is not particularly limited as long as it is appropriately set according to the purpose and use, and is usually preferably 10 to 90% by mass, and more preferably 20 to 80% by mass based on the entire photosensitive resin composition. .

(O) colored materials

In the colored material, the photosensitive resin composition of the present invention is colored to further form a photosensitive colored resin composition, and the same coloring material as that shown as an essential component of the colored material dispersion composition of the present invention can be used.

The ratio of the coloring material in the photosensitive resin composition of the present invention may be appropriately set according to the purpose and use, and in terms of the balance between the coloring power and the dispersion stability, (N) in the self-photosensitive resin composition. The component other than the solvent is usually preferably from 3 to 70% by mass, more preferably from 5 to 60% by mass, still more preferably from 10 to 50% by mass.

(P) Other ingredients

In the photosensitive resin composition of the present invention, a filler, a binder resin other than the alkali-soluble resin of the present invention, a dispersant, a heat-resistant enhancer, a development aid, and a plasticizer may be formulated according to the purpose of each use or required characteristics. , polymerization inhibitors, UV absorbers, antioxidants, matting agents, defoamers, leveling agents, antistatic agents, dispersants, smoothing agents, surface modifiers, thixotropic agents, thixotropic agents, decane systems or A component other than the above-mentioned essential components, such as a coupling agent such as an aluminum-based or titanium-based compound, a quinonediazide compound, a polyhydric phenol compound, a cationically polymerizable compound, and an acid generator. Hereinafter, other components which are suitable when the photosensitive resin composition of the present invention is used as a resist for a color filter will be described.

<Adhesive resin other than alkali-soluble resin of the present invention>

In order to adjust the balance of various characteristics of the color filter resist, or to reduce the cost of the resist, etc., an adhesive resin other than the alkali-soluble resin of the present invention can be used. Specific examples of such a binder resin include (meth)acrylic acid/(meth)acrylate copolymer, (meth)acrylic acid/aromatic vinyl copolymer, and (meth)acrylic acid/(A). Acrylate/aromatic vinyl copolymer, (meth)acrylic acid/(meth)acrylate copolymer/N-substituted maleimide copolymer, (meth)acrylic acid/aromatic vinyl/ N-substituted maleimide copolymer, (meth)acrylic acid/(meth)acrylate/polystyrene macromonomer copolymer, etc. (meth)acrylic copolymer; (meth)acrylic acid copolymer A vinyl ester type alkali-soluble resin obtained by adding a radical polymerizable unsaturated group to a side chain, a (meth)acrylic acid to an epoxy resin, and further reacting a polybasic acid anhydride.

The amount of the binder resin other than the alkali-soluble resin of the present invention is not particularly limited as long as it is characteristic of the alkali-soluble resin of the present invention, and may be appropriately set according to the purpose and use, and it is preferred to use a photosensitive resin. The proportion of the alkali-soluble resin of the present invention among all the binder resins contained in the composition is 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more.

<dispersant>

When a coloring material is added to the photosensitive resin composition of the present invention to form a photosensitive colored resin composition, the dispersing agent is preferably formulated as a component together with the above-mentioned essential components. As the dispersing agent, the same dispersing agent as the essential component of the above-described colored material dispersion composition of the present invention can be used.

The ratio of the dispersing agent in the photosensitive resin composition of the present invention may be appropriately set according to the purpose and use, and in order to achieve dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) or transparency, The amount of the colored material is usually preferably from 0.01 to 60% by mass, more preferably from 0.1 to 50% by mass, even more preferably from 0.5 to 40% by mass.

<heat-resistant lifting agent>

In the photosensitive resin composition of the present invention, in order to improve heat resistance and strength, a N-(alkoxymethyl)melamine compound or a compound having two or more epoxy groups or oxetanyl groups may be added. In particular, when a resist for a photo-spacer, a transparent resist for a protective film, or a resist for an interlayer insulating film is formed, it is preferred to use these compounds.

<homogening agent>

In the photosensitive resin composition of the present invention, a leveling agent may be added in order to improve the homogenization property. As the leveling agent, a fluorine-based or lanthanide-based surfactant is preferred.

<coupling agent>

In the photosensitive resin composition of the present invention, a coupling agent may be added in order to improve the adhesion. The coupling agent is preferably a decane-based coupling agent, and specific examples thereof include an epoxy-based, methacrylic-based or amine-based decane coupling agent. Among them, an epoxy-based decane coupling agent is preferred.

<Development Aid>

In the photosensitive resin composition of the present invention, in order to improve developability, the following compounds may be added as a development aid: monocarboxylic acids such as (meth)acrylic acid, acetic acid, and propionic acid; maleic acid and fumarate; Polycarboxylic acids such as acid, succinic acid, tetrahydrophthalic acid, and trimellitic acid; carboxylic anhydrides such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride.

The photosensitive resin composition of the present invention can be an alkali-soluble resin, a radically polymerizable monomer, a photoinitiator, a solvent, an optional colored material, a dispersing agent, or the like of the present invention by using various mixers or dispersing machines. It is prepared by mixing and dispersing other essential components such as a binder resin and a leveling agent.

When the photosensitive resin composition of the present invention contains a colored material, it is produced by a dispersion treatment step of a colored material. For example, firstly weigh a predetermined amount of the colored material, dispersant, binder resin, solvent, and use a paint regulator, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, a blender, etc. The machine disperses the colored material to form a liquid colored material dispersion (grinding slurry). Preferably, the mixture is subjected to kneading dispersion treatment using a roll mill, a kneader, a blender, or the like, and then subjected to a micro-dispersion treatment using a media mill such as a bead mill filled with beads of 0.01 to 1 mm. To the obtained slurry, a transparent resist liquid containing a radical polymerizable monomer, a photoinitiator, a binder resin, a solvent, a homogenizing agent, or the like, which is separately stirred and mixed, is added and mixed to obtain a uniform dispersion solution. A photosensitive colored resin composition was obtained. It is preferable that the obtained photosensitive colored resin composition is subjected to a filtration treatment by a filter or the like to remove fine waste.

The present invention is also a color filter having a section formed using the above-described photosensitive resin composition. Examples of the method of forming the color filter segments (black matrix, red, green, and blue pixels, light spacers, protective layers, alignment control ribs, etc.) include photolithography, printing, and electricity. In the photolithography method, a method of using a negative-type acrylic photosensitive resin composition (photosensitive acrylic method) and a non-photosensitive polyimine-based resin are used as a photolithography method. Method of positive and positive resist (non-photosensitive polyimine method). In the photosensitive acrylic method, specifically, a negative photosensitive resin composition is applied onto a support substrate and dried, and a mask is placed on the formed coating film, and exposure is performed through the mask to expose the exposed portion. A method of curing, developing an unexposed portion, cleaning as necessary, and further performing thermal curing or photohardening treatment to form segments of the respective color filters. In particular, when the support substrate is large, coating by a slit coating device is usually performed. When the photosensitive resin composition of the present invention is used as the negative photosensitive resin composition, a segment of a high-quality color filter can be formed with good yield. Moreover, the excellent dry resolubility of the alkali-soluble resin and the photosensitive resin composition of the present invention can be exerted, and it can be applied to a section of a color filter by an inkjet method.

In the case of a color filter, in the case of a liquid crystal display device, when a pixel is formed on a transparent substrate and used for an image pickup device element, it is necessary to form a pixel on the photoelectric conversion element substrate, as needed. A black matrix that separates each pixel may be formed, or a protective film may be formed on the pixel, or a light spacer may be formed on the black matrix region, or ITO (Indium Tin Oxide) may be formed on the pixel or the protective film. The transparent electrode or the structure for forming an alignment film and alignment control. Further, a black matrix and a pixel may be formed on a transparent substrate on which a TFT (Thin-Film Transistor) is formed, and a protective film, a photo spacer, or the like may be formed as needed.

The color filter of the present invention may be formed by using at least one segment formed using the photosensitive resin composition of the present invention, and it is preferable that all the colors of the pixel are formed using the photosensitive resin composition of the present invention. Preferably, the black matrix and the pixel are formed using the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention is particularly suitable for use as a pixel to be colored and a black matrix, and is also suitable for forming a segment which does not require coloring, such as a photo spacer or a protective layer.

Examples of the transparent substrate include, in addition to glass, thermoplastic plastic sheets such as polyester, polycarbonate, polyolefin, polyfluorene, a ring-opening polymer of a cyclic olefin, or a hydrogenated product thereof, an epoxy resin, and an unsaturated polyester. The thermosetting plastic sheet such as a resin is preferably a glass plate or a heat-resistant plastic sheet from the viewpoint of heat resistance. Further, the transparent substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment using a decane coupling agent or the like as necessary.

The black matrix is formed on a transparent substrate using a metal thin film or a photosensitive colored resin composition for a black matrix. The black matrix using the metal thin film is formed, for example, by a single layer of chromium or two layers of chromium and chromium oxide. At this time, first, a thin film of the above metal or metal ‧ metal oxide is formed on a transparent substrate by vapor deposition, sputtering, or the like. Then, after forming a positive photosensitive film thereon, the photosensitive film was exposed and developed using the photomask to form a black matrix image. Then, the film is etched to form a black matrix. When a photosensitive colored resin composition for a black matrix is used, a black matrix is formed in accordance with the above-described formation by a photosensitive acrylic method.

The pixels are usually three colors of red, green, and blue. For example, a green photosensitive coloring composition is first used, and a green pixel is formed in accordance with the above-described formation by a photosensitive acrylic method. This operation is also performed for the remaining two colors to form three-color pixels. The order in which the pixels of the respective colors are formed is not particularly limited.

The protective film is formed on the pixel by forming a transparent photosensitive resin composition for a protective film after forming a pixel, in accordance with the above-described formation by a photosensitive acrylic method. In order to achieve cost reduction and simplification of the steps, a protective film is sometimes not formed.

When a transparent electrode is formed on a pixel or a protective film, indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or the like, or the like may be used, by sputtering, vacuum evaporation, or the like. A film is formed by a CVD (Chemical Vapor Deposition) method or the like, and a predetermined pattern is formed by etching using a positive resist or using a jig as necessary. In some liquid crystal driving methods such as a planar alignment type driving method (IPS (In-Plane Switching) mode), a transparent electrode may not be formed.

The light-receiving member is formed by using a photosensitive resin composition for a light-receiving member as needed, and is formed on the black matrix directly or in accordance with the black matrix region to form a protective film or a black matrix region. On the transparent electrode. Sometimes, no light spacers are formed, and the cell gap is maintained by the particulate spacers.

Examples of the method of applying the photosensitive resin composition onto the substrate include spin coating, slit coating, roll coating, and cast coating. In particular, when the photosensitive resin composition of the present invention is used, It is better to use the method of slit coating. The coating conditions for the slit coating differ depending on the slit and the rotation method, the non-rotation method, the size of the transparent substrate, the target film thickness, and the like, and the discharge amount from the nozzle and the moving speed of the slit head are appropriately selected. Further, the lip width at the tip end of the nozzle is usually set to 30 to 500 μm, and the distance between the tip end of the nozzle and the substrate is usually set to 30 to 300 μm. Further, the photosensitive resin composition of the present invention can also be preferably applied to a method using spin coating, roll coating, or cast coating. The film thickness of the coating film is usually 0.3 to 3.5 μm in the case of a black matrix, a pixel, and a protective film, and is usually 1 to 10 μm in the case of a light spacer.

The drying of the coating film after application on the substrate is carried out using a hot plate, an IR (infrared) oven, a convection oven, or the like. The drying conditions are appropriately selected depending on the boiling point of the solvent component contained, the type of the hardening component, the film thickness, the performance of the dryer, and the like, and are usually carried out at a temperature of 50 to 160 ° C for 10 seconds to 300 seconds.

The exposure is a step of irradiating the coating film with active light through a predetermined mask pattern. As the light source of the active light, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a fluorescent lamp, etc., an argon lamp can be used. Laser lasers such as ion lasers, YAG lasers, excimer lasers, nitrogen lasers, xenon-cadmium lasers, and semiconductor lasers. Examples of the exposure machine include a proximity mode, a mirror projection method, and a stepping method, and a proximity mode can be preferably used.

After the exposure, the development treatment is performed by the developer to remove the unexposed portion to form a pattern. The developer can be used as long as it dissolves the photosensitive resin composition of the present invention, and an organic solvent or an alkaline aqueous solution is usually used. When an alkaline aqueous solution is used as the developing solution, it is preferred to further wash with water after development. The alkaline aqueous solution may contain, in addition to the alkaline agent, a surfactant, an organic solvent, a buffer, a dye, a pigment, or the like. Examples of the alkaline agent include inorganic alkaline agents such as sodium citrate, potassium citrate, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, disodium phosphate, sodium carbonate, potassium carbonate, and sodium hydrogencarbonate. An amine such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide or tetraethylammonium hydroxide, which may be a single one or a Two or more combinations. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, sulfosuccinates; alkylbetaines, amines An amphoteric surfactant such as a basic acid or the like may be used alone or in combination of two or more. Examples of the organic solvent include alcohols such as isopropyl alcohol, benzyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol. These may be used alone or in combination of two or more. The development treatment is usually carried out by a method such as immersion development, spray development, brush development, ultrasonic development, or the like at a development temperature of 10 to 50 °C.

After development, it is usually heated at a temperature of 150 to 250 ° C for 5 to 60 minutes using a heating apparatus such as a hot plate, a convection oven, or a high-frequency heater to perform a heat hardening treatment.

The color liquid crystal display panel of the present invention is provided with the above-described color filter liquid crystal display panel of the present invention. The liquid crystal display panel of the present invention can be produced, for example, by forming an alignment film on the inner surface side of the color filter, and sealing the liquid crystal compound in the gap portion with the counter substrate.

As the alignment film, a resin film such as polyimide or the like is suitable, and is usually subjected to surface treatment by ultraviolet treatment or rubbing treatment after coating or thermal firing. The liquid crystal compound is not particularly limited, and those which are generally used can be used. Suitable for the counter substrate is a TFT substrate, which can be manufactured by a usual method. The bonding gap between the color filter and the counter substrate is usually in the range of 2 to 8 μm. After bonding the counter substrate, the liquid crystal display panel is completed by sealing with a sealing material.

According to the present invention, it is possible to provide the above-mentioned AMA copolymer which exhibits curability (oxygen scavenging property) in air, good adhesion, transparency, and heat resistance, and has a structural unit represented by the formula (1) in the main chain. (b). Further, in the method for producing the AMA copolymer (b), the branching of the polymer can be suppressed in the radical polymerization of the AMA monomer (a), and abnormal polymerization or gelation can be prevented, so that it can be provided. It is easy to adjust the physical properties according to the application or to provide various functions, and has good manufacturing stability and can perform strict quality management. It is suitable for optical applications or resisting materials, etc., which are highly demanding in various functions and strict quality management. An allyloxy methacrylic copolymer. Thus, the α-allyloxy methacrylic acid copolymer obtained by the production method of the present invention and the resin having the structural unit represented by the formula (1) in the main chain obtained by a method other than the production method of the present invention are used. In comparison, heat resistance becomes high, and it is more suitable for applications requiring heat resistance.

Further, the radically curable resin composition of the present invention can provide a radical curable resin which is excellent not only in air curability (oxygen scavenging property) but also excellent in adhesion and transparency, and is excellent in heat resistance. Composition. Therefore, the radical curable resin composition of the present invention is particularly suitable for applications requiring heat resistance in various applications using a radical-curable composition, such as a sealing material for an electronic component, an overcoat layer, and a coating. Materials or adhesives, solder resists, color filter resists, lenses for electronic parts, molding materials, and the like.

According to the colored material dispersion composition of the present invention, it is possible to provide a colored material dispersion composition which is highly dispersible and has other properties such as adhesion, hardenability and the like, and is also a constituent of the dispersion composition of the colored material. The adhesive resin of the present invention is also excellent in production stability.

According to the photosensitive resin composition of the present invention, an alkali-soluble resin which is excellent in dispersibility of heat resistance and coloring material and excellent in plate-making property, and a photosensitive resin composition using the resin can be provided. Since the photosensitive resin composition is excellent in heat resistance, it is suitable for forming a resist for a member in the field of electronic information, such as a solder resist, an etching resist, an interlayer insulating material, a plating resist, and a resist for a color filter. Since the dispersibility of the colored material is also excellent, it is particularly suitable for forming a color layer of a color filter.

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. In addition, unless otherwise indicated, "parts" means "parts by weight" and "%" means "mass%".

<analysis>

The analysis of this example was carried out as follows.

(Mw, Mn, Mw/Mn)

The resin solution was diluted with tetrahydrofuran and filtered using a filter having a pore size of 0.45 μm, and the obtained filter was measured by the following gel permeation chromatography (GPC) apparatus and conditions.

Device: HLC-8220GPG (manufactured by Dongfang Company)

Dissolution solvent: tetrahydrofuran

Standard material: Standard polystyrene (manufactured by Dongfang Company)

Separation column: TSKgel Super HZM-M (manufactured by Toki Co., Ltd.).

(average number of functional groups)

Average functional group number = Mn × { (weight of AMA-R in monomer composition)

Proportion [% by mass] / 100) × (1/Molecular weight of AMA-R)}.

(polymerization concentration)

Polymerization concentration [% by mass] = total amount of monomers used in polymerization / (total amount of monomers used in polymerization + total amount of solvent used in polymerization) × 100

(removal of resin)

A part of the resin solution was diluted with tetrahydrofuran, and poured into an excess amount of hexane to carry out reprecipitation. After the precipitate was taken out by filtration, vacuum drying (5 hours or more) was carried out at 70 ° C, whereby a white powder of the resin was obtained.

( ¹ H-NMR measurement)

200 mg of the white powder obtained as described above was dissolved in 3 g of deuterated dimethyl hydrazine containing tetramethyl decane, and measured by a nuclear magnetic resonance apparatus (200 MHz, manufactured by Varian Co., Ltd.).

(solid content)

About 0.3 g of the resin solution was weighed in an aluminum cup, and after adding about 2 g of acetone to dissolve it, it was naturally dried at normal temperature. After drying at 140 ° C for 3 hours using a hot air dryer, it was left to cool in a desiccator, and the weight was measured. The solid content of the resin solution was calculated from the weight reduction amount.

(thermogravimetric analysis)

The polymer (resin) powder obtained by reprecipitation was measured under the following measuring equipment and conditions to obtain a dynamic TG curve. A 5% weight loss temperature was obtained from the obtained TG curve.

Device: Thermo Plus TG8120 (manufactured by Physicochemical Co., Ltd.)

Environment: nitrogen flow 100 ml / min

Heating conditions: stepped constant temperature control (SIA mode), heating rate = 10 ° C / min, mass change speed value = 0.005% / sec

(resin acid value)

The acid value of the polymer (resin) solution was measured by an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., COM-555) using a KOH aqueous solution of 0.1 as a titration solution. The acid value of the solid component is calculated from the acid value of the solution and the solid content, and is taken as the acid value of the resin.

<Synthesis of a monomer represented by the formula (2)>

[Synthesis Examples 1 to 5]

According to Japanese Patent Laid-Open No. Hei 10-226669, 1,4-diazabicyclo[2.2.2]octane is used as a catalyst, as shown in Table 1, from allyl alcohol and corresponding α-hydroxymethyl groups. Acrylate (HMA-R) to synthesize each α-allyloxy methacrylate (AMA-R) of the monomer represented by the formula (2).

<aggregation>

[Example 1]

A thermometer, a condenser, a gas introduction tube, and a stirring device were attached to a four-port separable flask as a reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Under a nitrogen stream, 213.5 parts of propylene glycol monomethyl ether acetate (PGMEA) was added to the reaction vessel, and the temperature was raised to 90 °C. On the other hand, 121.8 parts of AMA-M and 78.2 parts of methyl methacrylate (MMA) obtained in Synthesis Example 1 were prepared in the dropping tank A, and 2-ethylhexyl peroxide was prepared in the dropping tank B. 4.7 parts of acid tert-butyl ester (PBO) and 42.0 parts of PGMEA were stirred and mixed, and 3.5 parts of methyl 3-mercaptopropionate (MPM) and 44.5 parts of PGMEA were prepared by stirring in a dropping tank C.

After confirming that the internal temperature of the reaction tank was stabilized, the respective mixtures were added dropwise from the dropping tanks A, B, and C, and the internal temperature was adjusted to 90 ° C, and the tank A was dripped for 3 hours from the dropwise addition tank B. The polymerization was carried out by dropwise addition over 4 hours from dropwise addition of C over 3.5 hours. After the completion of the dropwise addition, the temperature was raised and the temperature was raised to 115 °C. After maintaining at 115 ° C for 1 hour, it was cooled to room temperature to obtain a resin solution. Further, a white powder of a resin was obtained by the above reprecipitation operation. The analysis results are shown in Table 2.

[Embodiment 2]

A thermometer, a condenser, a gas introduction tube, and a stirring device were attached to a three-neck separable flask as a reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Under a nitrogen stream, 150.0 parts of PGMEA was added to the reaction vessel, and the temperature was raised to 90 °C. On the other hand, in the dropping tank, 60.9 parts of AMA-M, 39.1 parts of MMA, and 6.0 parts of PBO were prepared by stirring and mixing.

After confirming that the internal temperature of the reaction vessel was stabilized, the mixture was dropwise added from the dropwise addition tank, and the internal temperature was adjusted to 90 ° C while dropwise addition for 3 hours to carry out a polymerization reaction. After 60 minutes from the end of the dropwise addition, the temperature was raised and the temperature was raised to 115 °C. After maintaining at 115 ° C for 1 hour, it was cooled to room temperature to obtain a resin solution. The analysis results are shown in Table 2.

[Example 3]

A resin solution and a white powder of a resin were obtained in the same manner as in Example 1 except that 60.0 parts of AMA-M and 140.0 parts of MMA were prepared in the dropping tank A. The analysis results are shown in Table 2.

[Example 4]

A thermometer, a condenser, a gas introduction tube, and a stirring device were attached to a three-neck separable flask as a reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Under a nitrogen stream, 120.1 parts of PGMEA was added to the reaction vessel, and the temperature was raised to 90 °C. On the other hand, in the dropping tank A, 30.0 parts of AMA-M, 70.0 parts of MMA, and 6.0 parts of PBO were prepared by stirring, and 3-mercaptopropionic acid (MPA) 0.1 was prepared in the dropping tank B. The mixture was mixed with PGMEA 29.9 parts.

After confirming that the internal temperature of the reaction tank was stabilized, the mixture was gradually added dropwise from the dropping tanks A and B, and the internal temperature was adjusted to 90 ° C, and 90 minutes from the dropping tank A and 150 times from the dropping tank B. The mixture was added dropwise in a minute to carry out a polymerization reaction. After 30 minutes from the end of the dropwise addition of the dropping tank A, the temperature was raised and the temperature was raised to 115 °C. After maintaining at 115 ° C for 1 hour, it was cooled to room temperature to obtain a resin solution. The analysis results are shown in Table 2.

[Example 5]

A thermometer, a condenser, a gas introduction tube, and a stirring device were attached to a three-neck separable flask as a reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Under a nitrogen stream, 150.0 parts of PGMEA was added to the reaction vessel, and the temperature was raised to 90 °C. On the other hand, in the dropping tank, 3 parts of AMA-M, 70.0 parts of MMA, and 6.0 parts of PBO were prepared by stirring and mixing.

After confirming that the internal temperature of the reaction vessel was stabilized, the mixture was dropwise added from the dropping tank, and the internal temperature was adjusted to 90 ° C while dropwise addition for 90 minutes to carry out a polymerization reaction. After 30 minutes from the end of the dropwise addition, the temperature was raised and the temperature was raised to 115 °C. After maintaining at 115 ° C for 1 hour, it was cooled to room temperature to obtain a resin solution. The analysis results are shown in Table 2.

[Embodiment 6]

A thermometer, a condenser, a gas introduction tube, and a stirring device were attached to a four-port separable flask as a reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Under a nitrogen stream, 223.7 parts of PGMEA was added to the reaction vessel, and the temperature was raised to 90 °C. On the other hand, in the dropping tank A, 180.0 parts of AMA-M obtained in Synthesis Example 1 and 20.0 parts of methacrylic acid (MAA) were mixed and mixed, and 4.7 parts of PBO was prepared in the dropping tank B. The mixture was stirred and mixed with 36.3 parts of PGMEA, and 3.0 parts of MPA and 39.0 parts of PGMEA were mixed and stirred in the dropping tank C.

After confirming that the internal temperature of the reaction tank was stabilized, the respective mixtures were added dropwise from the dropping tanks A, B, and C, and the internal temperature was adjusted to 90 ° C, and the tank A was dripped for 3 hours from the dropwise addition tank B. And C was added dropwise over 3.5 hours to carry out a polymerization reaction. After 30 minutes from the end of the dropwise addition, the temperature was raised and the temperature was raised to 115 °C. After maintaining at 115 ° C for 1 hour, it was cooled to room temperature to obtain a resin solution. Further, a white powder of a resin was obtained by the above reprecipitation operation. The analysis results are shown in Table 2.

[Embodiment 7]

Except that the mixed liquid prepared in the dropping tank A was changed to AMA-M 120.0 parts, benzyl methacrylate (BZMA) 50.0 parts, MMA 1.4 parts, and MAA 28.6 parts were thoroughly stirred and mixed, and Examples 6 A white powder of a resin solution and a resin was obtained in the same manner. The analysis results are shown in Table 2.

[Embodiment 8]

A resin solution and a resin were obtained in the same manner as in Example 6 except that the mixed liquid prepared in the dropping tank A was changed to a mixture of AMA-M 60.0 parts, BZMA 110.0 parts, MMA 1.4 parts, and MAA 28.6 parts. White powder. The analysis results are shown in Table 2.

Further, ¹ H-NMR was measured using the obtained resin powder. The ¹ H-NMR curve is shown in Fig. 1 .

[Embodiment 9]

A resin solution was obtained in the same manner as in Example 6 except that the mixed liquid prepared in the dropping tank A was changed to a mixture of AMA-M 20.0 parts, BZMA 110.0 parts, MMA 41.4 parts, and MAA 28.6 parts. The analysis results are shown in Table 2.

[Examples 10 to 13]

A resin solution was obtained in the same manner as in Example 8 except that the type of AMA-R prepared as a monomer for introducing an ether ring structure in the dropping tank A was changed to that shown in Table 2. The analysis results are shown in Table 2.

[Embodiment 14]

The mixture was prepared by changing the mixed liquid prepared in the dropping tank A to 60.0 parts of AMA-M, 110.0 parts of cyclohexyl methacrylate (CHMA), 1.4 parts of MMA, and 28.6 parts of MAA. 6 A resin solution was obtained in the same manner. The analysis results are shown in Table 2.

[Example 15]

A thermometer, a condenser, a gas introduction tube, and a stirring device were attached to a four-port separable flask as a reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Under a nitrogen stream, 208 parts of PGMEA was added to the reaction vessel, and the temperature was raised to 90 °C. On the other hand, 96.8 parts of styrene (ST) was prepared in the dropping tank A, and 60.0 parts of AMA-M, 1.4 parts of MMA, 28.6 parts of MAA, and 5.0 parts of PBO were sufficiently stirred and mixed in the dropping tank B. In the dropping tank C, 3.0 parts of MPA and 92.0 parts of PGMEA were thoroughly stirred and mixed.

After confirming that the internal temperature of the reaction vessel was stabilized, 13.2 parts of ST was charged into the reaction tank, and immediately after the dropwise addition of the tanks A, B, and C, the respective mixtures were dropwise added, and the internal temperature was adjusted to 90 ° C while self-drip. The addition of the tank A was carried out for 8 hours, and dropwise addition was carried out for 10 hours from the dropwise addition tanks B and C to carry out a polymerization reaction. One hour after the completion of the dropwise addition, the temperature was raised and the temperature was raised to 115 °C. After maintaining at 115 ° C for 1 hour, it was cooled to room temperature to obtain a resin solution. Further, a white powder of a resin was obtained by the above reprecipitation operation. The analysis results are shown in Table 2.

[Example 16]

A thermometer, a condenser, a gas introduction tube, and a stirring device were attached to a four-port separable flask as a reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Under a nitrogen stream, 150.0 parts of PGMEA and 14.0 parts of 2-propanol (IPA) were added to the reaction vessel, and the temperature was raised to 90 °C. On the other hand, in the dropping tank A, 48.0 parts of AMA-M, 64.0 parts of BZMA, and 48.0 parts of MAA were prepared by stirring, and in the dropping tank B, 3.7 parts of PBO and 38.3 parts of PGMEA were mixed and mixed. As a result, in the dropping tank C, 4.3 parts of MPA and 37.7 parts of PGMEA were mixed and mixed.

After confirming that the internal temperature of the reaction tank was stabilized, the respective mixtures were added dropwise from the dropping tanks A, B, and C, and the internal temperature was adjusted to 90 ° C, and the tank A was dripped for 3 hours from the dropwise addition tank B. And C was added dropwise over 3.5 hours to carry out a polymerization reaction. After 30 minutes from the end of the dropwise addition, the temperature was raised, and the temperature was raised to 115 ° C. The temperature was maintained at 115 ° C for 1 hour, and then cooled to room temperature.

The introduction gas was changed from nitrogen to a nitrogen/oxygen mixed gas (oxygen 7%), 0.06 part of 6-t-butyl-2,4-xylenol (TBXL), and 52.8 parts of glycidyl methacrylate (GMA). In the order of 0.6 parts of dimethylbenzylamine (DMBA), the materials were added to the reaction vessel, and the mixture was stirred and heated. The internal temperature was adjusted to 110 ° C, and the side chain double bond introduction reaction was carried out. After maintaining at 110 ° C for 8 hours, the heating was temporarily stopped, and 80.0 parts of PGMEA was added, and the pressure in the system was gradually reduced to 37.3 kPa. Heating is resumed while maintaining the pressure, and the solvent containing IPA is distilled off, and the same amount of PGMEA as the amount of the solvent removed by distillation is supplied to the reaction tank to reduce the IPA contained in the solvent in the reaction tank. After the internal temperature reached 115 ° C, cooling began, and then the pressure was released to return the pressure in the system to normal pressure, and the distillation of the solvent was stopped, and the supply of PGMEA was also stopped. The cooling was continued until room temperature, and a resin solution was obtained. The analysis results are shown in Table 2.

Further, ¹ H-NMR was measured using a white powder of a resin obtained by the above reprecipitation operation. The ¹ H-NMR curve is shown in Fig. 2 .

[Example 17]

A resin solution was obtained in the same manner as in Example 16 except that 48.0 parts of AMA-M, 64.0 parts of CHMA, and 48.0 parts of MAA were stirred and mixed in the dropping tank A. The analysis results are shown in Table 2.

[Embodiment 18]

A thermometer, a condenser, a gas introduction tube, and a stirring device were attached to a four-port separable flask as a reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Under a nitrogen stream, 140.3 parts of PGMEA and 14.0 parts of IPA were added to the reaction vessel, and the temperature was raised to 90 °C. On the other hand, 56.3 parts of ST was prepared in the dropping tank A, and 48.0 parts of AMA-M, 48.0 parts of MAA, and 4.0 parts of PBO were prepared and mixed in the dropping tank B, and the mixture was mixed in the dropping tank C. Preparation has been made to mix 4.3 parts of MPA and 95.7 parts of PGMEA.

After confirming that the internal temperature of the reaction tank was stabilized, 7.7 parts of ST was charged into the reaction tank, and immediately after the dropwise addition of the tanks A, B, and C, the respective mixtures were dropwise added, and the internal temperature was adjusted to 90 ° C while self-drip. The addition of the tank A was carried out for 8 hours, and dropwise addition was carried out for 10 hours from the dropwise addition tanks B and C to carry out a polymerization reaction. One hour after the completion of the dropwise addition, the temperature was raised, and the temperature was raised to 115 ° C. The temperature was maintained at 115 ° C for 1 hour, and then cooled to room temperature.

The introduction gas was changed from nitrogen gas to a nitrogen/oxygen mixed gas (oxygen 7%), and each substance was added to the reaction tank in the order of 0.06 parts of TBXL, 52.8 parts of GMA, and 0.6 parts of DMBA, and then the mixture was stirred and heated. The temperature was adjusted to 110 ° C while the side chain double bond introduction reaction was carried out. After maintaining at 110 ° C for 8 hours, the heating was temporarily stopped, and 80.0 parts of PGMEA was added, and the pressure in the system was gradually reduced to 37.3 kPa. Heating is resumed while maintaining the pressure, and the solvent containing IPA is distilled off, and the same amount of PGMEA as the amount of the solvent removed by distillation is supplied to the reaction tank to reduce the IPA contained in the solvent in the reaction tank. After the internal temperature reached 115 ° C, cooling began, and then the pressure was released to return the pressure in the system to normal pressure, and the distillation of the solvent was stopped, and the supply of PGMEA was also stopped. The cooling was continued until room temperature, and a resin solution was obtained. The analysis results are shown in Table 2.

[Reference Example 1]

A white powder of a resin solution and a resin was obtained in the same manner as in Example 1 except that 200.0 parts of AMA-M was prepared in the dropping tank A. The analysis results are shown in Table 2. Further, the polymerization concentration was 40% by mass.

Further, the obtained resin powder was measured using ¹ H-NMR. The ¹ H-NMR curve is shown in Fig. 3 .

[Reference Example 2]

A thermometer, a condenser, a gas introduction tube, and a stirring device were attached to a three-neck separable flask as a reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Under a nitrogen stream, 170.5 parts of PGMEA was added to the reaction vessel, and the temperature was raised to 90 °C. On the other hand, in the dropping tank A, 50.0 parts of AMA-M and 1.0 part of PBO were prepared by stirring and mixing, and in the dropping tank B, 0.45 parts of MPM and 29.6 parts of PGMEA were prepared by stirring and mixing.

After confirming that the internal temperature of the reaction tank was stabilized, the mixture was gradually dropped from the dropping tanks A and B, and the internal temperature was adjusted to 90 ° C, and the tank A was used for 90 minutes from the dropping tank A and 150 minutes from the dropping tank B. The mixture was added dropwise to carry out a polymerization reaction. After 30 minutes from the completion of the dropwise addition of the dropping tank A, the temperature was raised and the temperature was raised to 115 °C. After maintaining at 115 ° C for 1 hour, it was cooled to room temperature to obtain a resin solution. The analysis results are shown in Table 2. Further, the polymerization concentration was 20% by mass.

The abbreviation in Table 2 is as follows.

A-M: α-allyloxymethyl methacrylate

A-CH: α-allyloxymethylcyclohexyl methacrylate

A-IB: α-allyloxyisobornyl methacrylate

A-BZ: α-allyloxybenzyl methacrylate

A-PE: phenoxyethyl methacrylate

MMA: Methyl methacrylate

BZMA: benzyl methacrylate

CHMA: cyclohexyl methacrylate

ST: Styrene

MAA: Methacrylic acid

PBO: tert-butyl peroxy-2-ethylhexanoate

MPM: methyl 3-mercaptopropionate

MPA: 3-mercaptopropionic acid

GMA: glycidyl methacrylate

MW: weight average molecular weight

Mn: number average molecular weight

Mw/Mn: molecular weight distribution

Further, in Table 2, the value of the monomer component indicates the content ratio (% by mass) in the monomer composition, and the values of the initiator, the chain transfer agent, and the GMA indicate the mass with respect to the total amount of the monomers used in the polymerization. proportion.

[Comparative Example 1]

A resin solution and a white powder of a resin were obtained in the same manner as in Example 1 except that 200.0 parts of tetrahydrofurfuryl methacrylate (THFM) was prepared in the dropping tank A. The analysis results are shown in Table 3.

[Comparative Example 2]

A resin solution and a white powder of a resin were obtained in the same manner as in Example 1 except that 200.0 parts of MMA was prepared in the dropping tank A. The analysis results are shown in Table 3.

[Comparative Example 3]

The amount of PGMEA added to the reaction tank was 163.7 parts, and the mixed liquid prepared in the dropping tank A was changed to 2,2'-[oxobis(methylene)]bis-2-acrylic acid. A resin solution and a white powder of a resin were obtained in the same manner as in Example 6 except that 60.0 parts of the ester (MD), 110.0 parts of BZMA, 1.4 parts of MMA, 28.6 parts of MAA, and 60.0 parts of PGMEA were sufficiently stirred and mixed.

The analysis results are shown in Table 3.

In addition, MD is a monomer which can obtain a resin having a tetrahydropyran ring in the main chain described in Non-Patent Document 1 and Patent Document 1.

[Comparative Example 4]

A thermometer, a condenser, a gas introduction tube, and a stirring device were attached to a four-port separable flask as a reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Under a nitrogen stream, 111.8 parts of PGMEA and 111.8 parts of IPA were added to the reaction vessel, and the temperature was raised until IPA refluxed and the internal temperature reached 89 °C. On the other hand, in the dropping tank A, 20.0 parts of MD, 110.0 parts of BZMA, 41.4 parts of MMA, and 28.6 parts of MAA were sufficiently stirred and mixed, and 4.7 parts of PBO and PGMEA 18.6 were prepared in the dropping tank B. A portion obtained by stirring and mixing IPA and 18.6 parts was prepared by mixing 3.0 parts of MPA, 19.5 parts of PGMEA, and 19.5 parts of IPA in the dropping tank C.

After confirming that the internal temperature and the reflux state of the reaction tank have stabilized, the respective mixtures are started to be added dropwise from the dropping tanks A, B, and C, and the mixture is added dropwise from the addition tank A for 3 hours, and the dropwise addition tanks B and C are used for 3.5 hours. , carrying out a polymerization reaction. After 30 minutes from the end of the dropwise addition, the temperature was raised, and the solvent containing IPA was distilled off, and the same amount of PGMEA as the amount of the solvent removed by distillation was supplied to the reaction vessel. After the internal temperature reached 115 ° C, the heating was temporarily stopped, and the pressure was gradually reduced to bring the pressure in the system to 37.3 kPa, and the pressure was maintained. When the pressure in the system reaches 37.3 kPa, the heating is started again, so that the internal temperature dropped by the decompression is again 115 ° C, the pressure is released and the pressure in the system is returned to the normal pressure, and the distillation of the solvent and the supply of PGMEA are stopped. . Further cooling was continued until room temperature, and a resin solution was obtained. The analysis results are shown in Table 3.

[Comparative Example 5]

In addition to changing the mixed liquid prepared in the dropping tank A, 60.0 parts of benzyl maleimide (BZMI), 110.0 parts of BZMA, 1.4 parts of MMA, 28.6 parts of MAA, and 60.0 parts of PGMEA were thoroughly stirred and mixed. A white powder of a resin solution and a resin was obtained in the same manner as in Example 6. The analysis results are shown in Table 3.

In addition, the BZMI is a monomer which is obtained as a resin having a ruthenium ring structure in a main chain, which is known as a resin having high heat resistance as described in Patent Document 2.

[Synthesis Example 6]

A resin solution and a white powder of a resin were obtained in the same manner as in Example 6 except that the mixed liquid prepared in the dropping tank A was changed to a mixture of 110.0 parts of BZMA, 1.4 parts of MMA6, and 28.6 parts of MAA. The analysis results are shown in Table 3.

[Synthesis Example 7]

A resin solution was obtained in the same manner as in Example 16 except that 48.0 parts of MMA was used instead of 48.0 parts of AMA-M. The analysis results are shown in Table 3.

The abbreviations in Table 3 are as follows except for the abbreviation in Table 2.

MD: 2,2'-[oxobis(methylene)] bis-2-acrylate dimethyl ester

BZMI: benzyl maleimide

THFM: tetrahydrofurfuryl methacrylate

Further, in Table 3, the numerical value of the monomer component indicates the content ratio (% by mass) in the monomer composition, and the values of the initiator, the chain transfer agent, and the GMA indicate the mass with respect to the total amount of the monomers used in the polymerization. proportion.

(Effect of the adhesive resin of the present invention on heat decomposition resistance)

From Examples 1 to 9, 15 and Reference Examples 1 and 2 and Comparative Example 1, it is understood that the adhesive resin of the present invention has a very high heat decomposition resistance as compared with the adhesive resin having a tetrahydroindenyl group in the side chain. Comparing with Comparative Example 3 and Comparative Example 5, the level was a known heat resistant resin (Comparative Example 3: a resin containing a tetrahydropyran ring in the main chain, and Comparative Example 5: a ruthenium ring contained in the main chain) Resin) The same degree of thermal decomposition resistance.

(Improvement of heat resistance by branch suppression)

From the comparison between Example 1 and Example 2 and the comparison of Examples 3, 4 and 8 with Example 5, it was found that by using a chain transfer agent, branching was suppressed and heat resistance was improved.

[Evaluation Example 1] Evaluation of a binder resin as a radical curable resin composition

[Examples 19 to 20, Reference Example 3, and Comparative Examples 6 to 7]

<Evaluation of the effect of reducing the inhibition of oxygen on polymerization (surface hardenability)>

As an index for evaluating the effect of reducing the inhibition of oxygen on polymerization, surface hardenability by photo-radical curing is used. In order to clearly evaluate the effect of the structural unit represented by the formula (1) on the surface hardenability, the conditions for easily suppressing the polymerization of oxygen (radical polymerizable monomer, photoradical polymerization initiator, blending ratio, The film thickness is performed under the film thickness.

(evaluation method)

1.2 parts of the powder of the binder resin described in Table 4, 2.8 parts of trimethylolpropane triacrylate (TMPTA), and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173, 0.2 parts of Ciba Specialty Chemicals Co., Ltd. and 6.0 parts of isopropyl acetate (IPAC) were stirred and mixed to form a homogeneous solution, which was applied to a floating glass using a bar coater. After naturally drying at room temperature for 10 minutes, it was dried at 70 ° C for 5 minutes using a hot air dryer to obtain a photoradical-curable coating film having a thickness of 10 μm. Then, the coating film was irradiated with UV using an ultrahigh pressure mercury lamp which can irradiate a certain amount of light, and the viscosity was confirmed by the surface of the finger. UV irradiation and finger touch were repeated, and the cumulative UV exposure amount [J/cm ² ] when the surface became non-sticky was recorded. The smaller the cumulative amount of UV irradiation, the better the surface hardenability. The results are shown in Table 4.

<Evaluation of adhesion>

One of the coating film properties after curing, in which the adhesion-based adhesive resin contributes a large amount, in order to unambiguously evaluate the effect of the structural unit shown in the formula (1) on the adhesion, it is evaluated only by the adhesive resin, and is used as a resin structure. A resin structure containing no acid group such as a carboxyl group or a strong base such as an amine.

Further, the resins of Examples 6 to 18 having an acid group were also excellent in adhesion.

(evaluation method)

The powder of the binder resin described in Table 4 was dissolved in IPAC to prepare a 39% solution. This was applied to a floating plate glass using a bar coater, and naturally dried at room temperature for 10 minutes, and then dried at 70 ° C for 5 minutes using a hot air dryer to obtain an adhesive resin coating film having a thickness of 10 μm. The adhesion of the coating film was evaluated in accordance with JIS K 5600-5-6 (cross cutting method) at a level of from 0 to 5. The results are shown in Table 4. Further, the classification criteria of the adhesion in Table 4 are shown in Table 5.

(Effect of the adhesive resin of the present invention on surface hardenability and adhesion)

According to the examples 19 and 20, the reference example 3, and the comparative example 7, it is understood that the surface hardening property and the adhesion property are improved by the structural unit represented by the formula (1), and it is understood from the comparative example 6 that the effect is in terms of surface hardenability. The resin has a higher degree of adhesion than the resin having a tetrahydroindenyl group in the side chain in the same degree as the resin having a tetrahydroindenyl group in the side chain.

[Examples 21 to 24, Reference Example 4, and Comparative Examples 8 to 9]

<Evaluation of transparency>

The powder of the binder resin described in Table 6 was dissolved in PGMEA to prepare a 30% solution, and the transmittance [%] of the solution at a wavelength of 400 nm was measured by a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation). As the transmittance before heating. On the other hand, the powder of the adhesive resin was placed in a glass container, heated at 230 ° C for 1.5 hours, dissolved in PGMEA to prepare a 30% solution, and the transmittance [%] at a wavelength of 400 nm was measured. Transmittance after heating. Further, using the transmittance before and after heating, the transmittance retention ratio [%] was calculated according to the following formula. The results are shown in Table 6.

Transmittance retention rate [%] = transmittance after heating / transmittance before heating × 100.

(Effect of the adhesive resin of the present invention on transparency)

From Examples 21 to 24, Reference Example 4, and Comparative Examples 8 to 9, it is understood that the binder resin of the present invention is compared with a binder resin having a tetrahydroindenyl group in a side chain and a resin having a quinone ring in the main chain. Has a high transparency.

[Evaluation Example 2] Evaluation of Adhesive Resin as a Colored Material Dispersion Composition

<Preparation of dispersion of colored material (polishing slurry) and evaluation of dispersion stability>

When evaluating the effect of the binder resin on the dispersion stability in the coloring resist, in general, in order to unambiguously evaluate the effect of the binder resin, it is evaluated by using a colored material dispersion liquid (polishing slurry) containing no hardening component, thereby preparing a slurry. The dispersion stability of the slurry was evaluated.

[Examples 25 to 32]

(Preparation of slurry)

First, as a dispersing agent solution, SOLSPERSE 24000GR (manufactured by Lubrizol Co., Ltd., hereinafter referred to as SP24000) was dissolved in PGMEA to 20%, and as a binder resin solution, the resin solution described in Table 7 was prepared to be diluted to 20% by PGMEA. By.

Then, CI Pigment Green 36 (Monastral Green 6Y-CL: manufactured by Heubach Co., Ltd., hereinafter referred to as PG36) 3.75 parts and CI Pigment Yellow 150 (Yellow Pigment E4GN-GT: manufactured by Lanxess Co., Ltd., hereinafter referred to as PY150) are used as the colored material. 2.5 parts, and 0.2 parts of SOLSPERSE 12000 (manufactured by Lubrizol Co., Ltd., hereinafter referred to as SP12000) as a dispersing agent were weighed into a 225 ml mayon bottle. Further, 3.75 parts of the above-mentioned 20% dispersant solution prepared in advance, 14.0 parts of the above 20% binder resin solution, 25.8 parts of PGMEA, and 50 parts of zirconia beads having a diameter of 1.0 mm were weighed into a 225 ml mayon bottle, and covered. . After the dispersion was treated by shaking with a paint shaker for 3 hours, the slurry was separated from the zirconia beads to obtain a slurry.

(confirmation of dispersion status)

The median diameter of the slurry immediately after the dispersion treatment was measured by a dynamic light scattering type particle size distribution measuring apparatus (LB-500, manufactured by Horiba, Ltd.), and the median diameter was 100 nm or less, and it was evaluated as ○, exceeding The 100 nm was evaluated as ×. The results are shown in Table 7.

(Evaluation of dispersion stability)

The dispersion state after the dispersion treatment is good (the median diameter is 100 nm or less) is stored in a constant temperature chamber (23 ° C), and the dispersion treatment is performed, and then a cone-and-plate type rotational viscometer (TVE22LT, Toki Sangyo Co., Ltd.) is used. Manufactured) The viscosity after 1 day, 2 weeks, and 4 weeks was measured. Further, the viscosity increase rate was calculated according to the following formula. The results are shown in Table 7.

Viscosity increase rate [%] = viscosity after 2 weeks (or after 4 weeks) / viscosity after 1 day × 100-100

[Example 33]

The preparation of the slurry and the evaluation of the dispersion stability were carried out in the same manner as in Example 25 except that the types and amounts of the components of the slurry filled in the mayon bottle were changed as follows. The results are shown in Table 7.

C.I. Pigment Blue 15:6 (Heliogen Blue L6700F: manufactured by BASF Corporation, hereinafter referred to as PB15:6): 5.0 parts

C.l. Pigment Violet 23 (Hostaperm Violet RL-NF, manufactured by Clariant, hereinafter referred to as PV23): 1.25 parts

20% PGMEA solution of SP24000: 3.75 parts

SP12000: 0.2 parts

The resin solution obtained in Example 8 was diluted to 20% with PGMEA: 14.0 parts

PGMEA: 25.8 parts.

[Example 34]

The preparation of the slurry and the evaluation of the dispersion stability were carried out in the same manner as in Example 25 except that the types and amounts of the components of the slurry filled in the mayon bottle were changed as follows. The results are shown in Table 7.

C.I. Pigment Red 254 (Irgaphor Red BT-CF: manufactured by Ciba Specialty Chemicals, hereinafter referred to as PR254): 4.4 parts

C.I. Pigment Red 177 (Cromophtal Red A3B: manufactured by Ciba Specialty Chemicals Co., Ltd., hereinafter referred to as PR177): 1.85 parts

20% PGMEA solution of SP24000: 5.0 parts

The resin solution obtained in Example 8 was diluted to 20% with PGMEA: 13.75 parts

PGMEA: 25.0 parts.

[Example 35]

The preparation of the slurry and the evaluation of the dispersion stability were carried out in the same manner as in Example 25 except that the types and amounts of the components of the slurry filled in the mayon bottle were changed as follows. The results are shown in Table 7.

Carbon black (MA220: manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as CB): 6.25 parts

20% PGMEA solution of SP24000: 3.75 parts

SP12000: 0.2 parts

The resin solution obtained in Example 8 was diluted to 20% with PGMEA: 14.0 parts

PGMEA: 25.8 parts.

[Comparative Examples 10 to 12]

The preparation of the slurry and the evaluation of the dispersion stability were carried out in the same manner as in Example 25 except that the resin solution was changed as shown in Table 7. The results are shown in Table 7.

(Effect of the alkali-soluble resin of the present invention on dispersion stability)

From Examples 25 and 26 and Comparative Example 12, it was found that the structural unit represented by the formula (1) improved the dispersion stability as compared with the conventional binder resin. Moreover, it is understood from Examples 25 and 26 and Comparative Examples 10 and 11 that the effect is higher than that of the resin having a tetrahydropyran ring in the main chain described in Non-Patent Document 1 and Patent Document 1. In addition, it is considered that the reason why the dispersion failure occurs in Comparative Example 10 is that the binder resin (Comparative Example 3) causes abnormal polymerization. Further, as is clear from Examples 27 to 32, even if the other copolymerization component is changed, even if the R of the structural unit represented by the formula (1) is changed, the dispersion stability is excellent.

[Evaluation Example 3] Evaluation as a binder resin for a photosensitive resin composition

<Evaluation of plate making>

A photosensitive colored resin composition (coloring resist) was prepared as follows, and the coloring resist was used to evaluate the plate making property. As an indicator of the plate making property, a development residue and a pattern shape are used.

[Example 36]

(Preparation of coloring resist)

First, each material for the slurry shown in Table 8 was subjected to dispersion treatment using a bead mill filled with zirconia beads of 0.3 mm to obtain a green slurry. Then, each of the materials for the transparent resist liquid shown in Table 8 was stirred and mixed to prepare a transparent resist liquid. 240.0 parts of the green slurry obtained in this manner and 135.0 parts of the transparent resist liquid were stirred and mixed, and then filtered using a filter of 1 μm to obtain a green resist.

(Evaluation of development residue and pattern shape)

Using a spin coater, the green coloring composition was applied to a 100 mm × 100 mm glass substrate on which a black matrix of chromium was formed by adjusting the rotation speed so that the film thickness after drying reached 1.5 μm, and then 90 Pre-bake at °C for 2 minutes. Further, exposure was performed at 100 mJ/cm ² by a proximity exposure machine and a pattern mask having a line and a gap of 10 μm in width. Thereafter, development was carried out with a 0.1% aqueous sodium carbonate solution using a spray developing device. Regarding the development time, development is carried out for a period of time between 10 and 100 seconds in which the most excellent developability is obtained. It is then washed with water and air dried. The obtained green substrate-attached glass substrate was observed with a laser microscope, and the development residue and pattern shape were evaluated by the following criteria. The results are shown in Table 9.

(1) Development residue

◎: There is no residue in the gap part.

○: There is a very small small residue in the gap portion.

△: The gap portion has a thin residue

×: There is a thick residue in the gap portion.

(2) Pattern shape

◎: The edge of the line is straight and clear

○: Some blurs at the edge of the line

△: the edges of the line are all blurred

×: The edges of the lines are noticeably jagged.

[Examples 37 to 42 and Comparative Examples 13 to 15]

The evaluation was carried out in the same manner as in Example 36 except that the adhesive resin for the polishing slurry and the adhesive resin for the transparent resist liquid were changed as shown in Table 9. The results are shown in Table 9.

(Effect of the alkali-soluble resin of the present invention on plate-making property)

It is understood that the plate-making property is improved by using the alkali-soluble resin of the present invention as a binder resin. In other words, when the photosensitive coloring resin composition of the present invention is used to form a segment of the color filter, the color filter can be produced with good yield.

<Color filter, and production of liquid crystal display panel>

[Example 43]

(Preparation of coloring resist)

The photosensitive colored resin composition of Example 41 was used as a green resist.

Further, in the same manner as in Example 41 except that the type and amount of the colored material were changed as shown in Table 10, a resist of each of red, blue, and black was obtained.

(Preparation of transparent resist for protective film for optical spacers)

Each of the materials shown below was stirred and mixed, and then filtered through a filter of 1 μm to obtain a transparent resist for a protective film for a photo-spacer.

The resin solution obtained in Example 16 was diluted to 20% with PGMEA: 100.0 parts

Dipentaerythritol hexaacrylate: 20.0 parts

Irgacure 907 (manufactured by Ciba Specialty Chemicals): 2.4 parts

Irgacure 369 (manufactured by Ciba Specialty Chemicals): 0.4 parts

PGMEA: 10.0 parts.

(Production of color filter and liquid crystal display panel)

The black resist was applied by a spin coating method on an alkali-free glass substrate of 230 mm × 300 mm and a thickness of 1.1 mm to form a coating film, and prebaking (80 ° C, 5 minutes). Thereafter, a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source was used, and an exposure amount of 500 mJ/cm ² was used for alignment exposure through a predetermined black matrix mask, development with an alkaline developer, and cleaning with pure water. After post-baking (230 ° C, 30 minutes), a black matrix (1.2 μm thick) was formed.

Then, the red resist was applied onto the substrate on which the black matrix was formed by spin coating to form a coating film, and prebaking (80 ° C, 5 minutes) was performed. Thereafter, using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source, the exposure amount of 100 mJ/cm ² was used for alignment exposure through a predetermined pixel, and development was carried out with an alkaline developing solution, followed by washing with pure water. Post-baking (220 ° C, 30 minutes) was performed to form a red pixel pattern (thickness of 2.0 μm). Similarly, a green pixel pattern is formed using a green resist, and a blue pixel pattern is formed using a blue resist.

The black matrix and the pixel pattern produced were examined by a laser microscope, and as a result, there was no pattern defect or development residue, and the surface smoothness of the pixel was also good.

On the substrate on which the black matrix and the pixels of the respective colors were formed, a coating film was formed by applying a transparent resist for a protective film for a photo spacer by a spin coating method, and prebaking (80 ° C, 5 minutes) was performed. Thereafter, using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source, the exposure amount of 100 mJ/cm ² was subjected to alignment exposure through a predetermined protective film with a photomask, development with an alkaline developing solution, and cleaning with pure water. After post-baking (220 ° C, 30 minutes), a protective film (thickness 1.5 μm) was formed.

A transparent conductive layer (thickness: 0.15 μm) made of indium tin oxide was formed on the color filter on which the protective film was formed by sputtering. On the substrate on which the protective film was formed, a coating film was formed by applying a transparent resist for a protective film for a photo spacer by a spin coating method, and prebaked (80 ° C, 5 minutes). Thereafter, a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source was used, and an exposure amount of 100 mJ/cm ² was used for alignment exposure with a mask through a predetermined spacer, and development was carried out with an alkaline developer to be washed with pure water. After post-baking (220 ° C, 30 minutes), a light spacer (having a height of 4.8 μm and a bottom of 12 μm × 12 μm square) was formed.

The color filter produced by the laser microscope was examined, and as a result, no defect of the spacer pattern or development residue was observed.

After the polyimine alignment layer is provided on the color filter prepared as described above and subjected to alignment treatment (friction), the epoxy resin sealing agent is bonded to the TFT array substrate, and the inlet is provided in the sealing portion. After a TN (Twisted Nematic) type liquid crystal is sealed between the color filter and the TFT array substrate, the injection port is sealed, and an optical film such as a polarizing plate is bonded to obtain a simple TN liquid crystal display device. .

The liquid crystal display device produced has high luminance and color purity, and can exhibit good display quality without causing color shift or the like.

[Industrial availability]

The radically curable resin composition of the present invention is excellent not only in air curability (oxygen scavenging property) but also in adhesion and transparency, and is excellent in heat resistance, and can be widely used as an adhesive, an adhesive, and Biomaterials, dental materials, optical components, information recording materials, materials for optical fibers, color filter resists, solder resists, plating resists, insulators, sealing materials, inkjet inks, printing inks, coatings, injection molding materials, Decorative panels, WPC, coated materials, photosensitive resin sheets, dry films, lining materials, civil construction materials, putties, maintenance materials, flooring materials, paving materials, gel coatings, outer coatings, hand coating/spraying /Stretching, filament winding, molding materials such as SMC/BMC, and polymer solid electrolyte.

The colored material dispersion composition of the present invention can highly coexist with dispersibility and other properties such as adhesion, heat resistance, surface hardenability, transparency, etc., and is particularly suitable for high-performance inks and coatings, for example, for automobiles and coated steel sheets. , building materials, cans, gravure, flexo, inkjet printers, color filters, etc.

The alkali-soluble resin of the present invention and the photosensitive resin composition of the present invention using the resin are excellent in heat resistance, and are suitable for forming a resist for a member in the field of electronic information, such as a solder resist, an etching resist, and an interlayer insulating layer. The material, the plating resist, and the color filter resist are excellent in dispersibility of the colored material and excellent in plate-making property, and therefore are particularly suitable for forming a color layer of a color filter.

Fig. 1 is a ¹ H-NMR chart measured using the resin powder obtained in Example 8.

Fig. 2 is a ¹ H-NMR chart measured using the resin powder obtained in Example 16.

Fig. 3 is a ¹ H-NMR chart measured using the resin powder obtained in Reference Example 1.

Claims (8)

An α-allyloxy methacrylic copolymer having a structural unit represented by the following formula (1) in its main chain, (wherein R represents a hydrogen atom, a chain-like saturated hydrocarbon group, an alkoxy-substituted chain-like saturated hydrocarbon group, a hydroxy-substituted chain-like saturated hydrocarbon group, an alicyclic hydrocarbon group, or an alicyclic hydrocarbon group, and a part of hydrogen atoms thereof are substituted by an alkoxy group or a hydroxyl group. An alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic hydrocarbon group in which a part of hydrogen atoms of an aromatic hydrocarbon group is substituted with an alkoxy group or a hydroxyl group). The α-allyloxy methacrylic acid copolymer according to the first aspect of the invention, wherein the α-allyloxy methacrylic copolymer is included in the formula (2) Obtained by the production method of the step of polymerizing the monomer component of the monomer, (wherein R represents a hydrogen atom, a chain-like saturated hydrocarbon group, an alkoxy-substituted chain-like saturated hydrocarbon group, a hydroxy-substituted chain-like saturated hydrocarbon group, an alicyclic hydrocarbon group, or an alicyclic hydrocarbon group, and a part of hydrogen atoms thereof are substituted by an alkoxy group or a hydroxyl group. An alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic hydrocarbon group in which a part of hydrogen atoms are substituted by an alkoxy group or a hydroxyl group). The α-allyloxy methacrylic acid copolymer according to the first aspect of the invention, wherein the α-allyloxy methacrylic copolymer is composed of α represented by the following formula (2) - an allyloxy methacrylic monomer and a monomer component of a radical polymerizable monomer other than the α-allyloxy methacrylic monomer; (wherein R represents a hydrogen atom, a chain-like saturated hydrocarbon group, an alkoxy-substituted chain-like saturated hydrocarbon group, a hydroxy-substituted chain-like saturated hydrocarbon group, an alicyclic hydrocarbon group, or an alicyclic hydrocarbon group, and a part of hydrogen atoms thereof are substituted by an alkoxy group or a hydroxyl group. An alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic hydrocarbon group in which a part of hydrogen atoms are substituted by an alkoxy group or a hydroxyl group). A resin composition comprising the α-allyloxy methacrylic copolymer according to any one of claims 1 to 3, and for use in a photosensitive application, a dispersible use of a colored material, and a radical At least one of the group consisting of a sclerosing use. A method for producing an α-allyloxymethyl methacrylate copolymer for producing an α-allyloxy methacrylic copolymer having a structural unit represented by the following formula (1) in a main chain: (wherein R represents a hydrogen atom, a chain-like saturated hydrocarbon group, an alkoxy-substituted chain-like saturated hydrocarbon group, a hydroxy-substituted chain-like saturated hydrocarbon group, an alicyclic hydrocarbon group, or an alicyclic hydrocarbon group, and a part of hydrogen atoms thereof are substituted by an alkoxy group or a hydroxyl group. An alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic hydrocarbon group in which a part of hydrogen atoms are substituted by an alkoxy group or a hydroxyl group, and the production method is characterized by comprising the step of: containing the following formula (2) The monomer component of the α-allyloxy methacrylic monomer is polymerized, (wherein R represents a hydrogen atom, a chain-like saturated hydrocarbon group, an alkoxy-substituted chain-like saturated hydrocarbon group, a hydroxy-substituted chain-like saturated hydrocarbon group, an alicyclic hydrocarbon group, or an alicyclic hydrocarbon group, and a part of hydrogen atoms thereof are substituted by an alkoxy group or a hydroxyl group. An alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic hydrocarbon group in which a part of hydrogen atoms are substituted by an alkoxy group or a hydroxyl group). The method for producing an α-allyloxymethyl acrylate copolymer according to claim 5, wherein the monomer component further contains the α-allyloxymethyl acrylate represented by the formula (2) A radical polymerizable monomer other than the monomer. The method for producing an α-allyloxymethyl acrylate copolymer according to claim 5, wherein the polymerization step comprises the step of performing radical polymerization in the presence of a chain transfer agent in a polymerization solvent. The method for producing an α-allyloxymethyl acrylate copolymer according to claim 7, wherein the chain transfer agent is a compound having a mercapto group.