JP6444159B2 - Polymer and its use - Google Patents

Description

  The present invention relates to a polymer and its use. More specifically, the present invention relates to a polymer and a polymer, a curable resin composition containing a polyfunctional (meth) acrylate, and a laminate.

  Conventionally, as a polymer having photopolymerizability excellent in heat resistance, for example, Patent Document 1 discloses a polymer obtained by polymerizing a monomer component containing maleimide, and Patent Document 2 discloses 2- ( Hydroxyalkyl) A polymer obtained by polymerizing a compound having a specific structure which is an ether dimer of an acrylate ester, and Patent Document 3 includes a polymer obtained by polymerizing a monomer component containing N-substituted maleimide and vinyltoluene. Proposed. Patent Document 4 proposes a polymer obtained by polymerizing an N-substituted maleimide, a carboxyl monomer, and a hydroxy monomer.

  In a resin composition containing a polymer derived from maleimide (maleimide polymer), since the maleimide polymer contains a nitrogen atom, the polymer is colored yellow to tan, and the cured film has transparency. There was a problem of becoming insufficient. This transparency problem is particularly noticeable when the thickness of the cured film is thick, and further, it may be further colored when heat-treated. On the other hand, a resin composition containing a polymer obtained by polymerizing a compound having a specific structure, which is an ether dimer of 2- (hydroxyalkyl) acrylic acid ester, together with a curing component has a coating film that is extremely excellent in heat resistance and transparency. Although it can be formed, there has been a case where improvement is required because the demand for the coloring level after the heat treatment is increasing year by year.

JP 2003-201316 A (3rd page etc.) JP 2004-300204 A (the third page etc.) JP 2009-040999 A (3rd page, etc.) JP 2004-302293 A (3rd page etc.)

  In view of the above situation, the present invention provides a polymer capable of forming a coating film having excellent heat resistance and transparency as well as curability, a curable resin composition using the polymer, the polymer, and the polymer. It aims at providing the laminated body using a curable resin composition.

  The inventors of the present invention have made various studies on the polymer. As a result, (a) a structural unit derived from an unsaturated monomer having an acid group, (b) a structural unit derived from an unsaturated monomer having a hydroxyl group, and (c) It has been found that a polymer containing a structural unit derived from an unsaturated monomer having an amino group as an essential component can solve the problem.

  Preferably, (a) an unsaturated monomer having a carboxyl group, (b) an unsaturated monomer having a hydroxyl group, and (c) an unsaturated monomer having an amino group are copolymerized as essential components. The present inventors have found that a polymer can solve the problem and have reached the present invention.

  More preferably, (a) a structural unit derived from an unsaturated monomer having an acid group, (b) a structural unit derived from an unsaturated monomer having a hydroxyl group, and (c) an unsaturated monomer having an amino group. It is a polymer containing a derived structural unit as an essential component, and the content ratio of the unsaturated monomer having an acid group is 0.5 to 50 with respect to the total of all monomer components constituting the polymer. The content of the unsaturated monomer having a hydroxyl group is 0.5 to 50% by mass, and the content of the unsaturated monomer having an amino group is 0.5 to 55% by mass. It is what.

Particularly preferably, the monomer component includes (a) an unsaturated monomer having a carboxyl group, (b) an unsaturated monomer having a hydroxyl group, and (c) an unsaturated monomer having an amino group. A polymer obtained by polymerization as an essential component, and the content of the unsaturated monomer having a carboxyl group is 0.5 to 50% by mass with respect to the total of all monomer components constituting the polymer, the hydroxyl group The content ratio of the unsaturated monomer containing is 0.5 to 50% by mass, and the content ratio of the unsaturated monomer having an amino group is 0.5 to 55% by mass. is there.
The polymer of the present invention preferably has a ring structure in the main chain.
A particularly preferred form for introducing a ring structure into the main chain is (d) the following general formula (1) as a monomer component.

(In formula (1), R ¹ and R ² each independently represents a hydrocarbon group selected from methyl, ethyl, cyclohexyl, and benzyl.)
(Monomer-derived structural unit), (e) N-substituted maleimide monomer (monomer-derived structural unit), and (f) α- (unsaturated alkoxyalkyl) acrylate system The polymer further comprises at least one monomer (structural unit) selected from monomers (structural units derived from monomers).

  The present invention is also a curable resin composition comprising the polymer, a polyfunctional (meth) acrylate, and practically a polymerization initiator.

  The present invention is also a laminate in which a cured layer formed by curing the polymer and / or the curable resin composition is provided on a substrate.

  The polymer and curable resin composition of the present invention can form a coating film having excellent heat resistance and transparency as well as curability. For example, resist materials, various coating agents, paints, etc. It can be suitably used in applications. Further, according to the present invention, it is possible to provide a laminate used for a display device having high luminance and color purity and good display quality that does not cause color unevenness.

The present invention is described in detail below.

The polymer of the present invention comprises (a) a structural unit derived from an unsaturated monomer having an acid group, (b) a structural unit derived from an unsaturated monomer having a hydroxyl group, and (c) an unsaturated group having an amino group. It is a polymer containing a monomer-derived structural unit as an essential component.
The structural unit derived from the unsaturated monomer corresponds to, for example, a structure (structural unit) in which a polymerizable double bond of each unsaturated monomer is opened by a polymerization reaction. The structure in which a polymerizable double bond is opened is, for example, a structure in which a carbon-carbon double bond (C═C) is a single bond (—C—C—). The acid group contained in the unsaturated monomer having an acid group is not particularly limited as long as it is a functional group that exhibits acidity in water, but a carboxyl group is preferable. As a preferred form, (a) an unsaturated monomer having a carboxyl group, (b) an unsaturated monomer having a hydroxyl group, and (c) an unsaturated monomer having an amino group are copolymerized as essential components. The polymer which becomes is mentioned. As a more preferable form, the content of unsaturated monomer having a carboxyl group is 0.5 to 50% by mass with respect to the total of all monomer components constituting the polymer, and the unsaturated monomer having a hydroxyl group. The polymer is characterized in that the content ratio of is from 50 to 50% by mass and the content ratio of the unsaturated monomer having an amino group is from 0.5 to 55% by mass. In addition, you may form the structural unit which has an acid group by making an acid anhydride react after superposing | polymerizing the unsaturated monomer which has a hydroxyl group.

  Although the use of the polymer of this invention is not specifically limited, Preferably it is used for binder resin for color resists, resin for solder resists, etc. The polymer of the present invention is a photosensitive alkali-soluble resin and exhibits good developability.

Among the acid groups that are essential components of the polymer of the present invention, examples of the unsaturated monomer having a carboxyl group include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (Meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, and the like, among these, (meth) acrylic Acid is preferred. The content ratio of the unsaturated monomer containing a carboxyl group is preferably in the range of 0.5 to 50% by mass, more preferably 2 to 50% by weight, and still more preferably 5 to 45% by weight in all monomer components. % Should be good. When the content of the unsaturated monomer containing a carboxyl group is less than 0.5% by mass, the solubility may be insufficient when the solubility by an alkaline substance is required. On the other hand, when the amount is more than 50% by mass, the solubility in a solvent may be lowered, or the viscosity of the polymer may be increased and the handling property may be deteriorated. In the present specification, “(meth) acrylic acid” is a notation expressing both methacrylic acid and acrylic acid.
Moreover, as an unsaturated monomer which has a hydroxyl group which is an essential component of the polymer of this invention, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid, for example Examples include 2-hydroxybutyl, (meth) acrylic acid mono (poly) ethylene glycol, (meth) acrylic acid mono (poly) propylene glycol, and the like. Among these, (meth) acrylic acid 2-hydroxyethyl, (meta) ) 2-Hydroxypropyl acrylate is preferred. The content ratio of the unsaturated monomer containing a hydroxyl group is preferably in the range of 0.5 to 50% by mass, more preferably 2 to 40% by weight, and still more preferably 5 to 30% by weight in all monomer components. It is good to be. If the content of the unsaturated monomer containing a hydroxyl group is less than 0.5% by mass, the heat resistance may be insufficient. On the other hand, when the amount is more than 50% by mass, the solubility in a solvent may be lowered, or the viscosity of the polymer may be increased and the handling property may be deteriorated.

  As an unsaturated monomer having an amino group which is an essential component of the polymer of the present invention, for example, the general formula (2)

(In Formula (2), R ³ has a hydrogen atom or a methyl group, and R ^{4 to} R ⁵ each independently have a hydrogen atom or a substituent and may have a chain or cyclic carbonization. Represents a hydrogen group, and R ⁴ and R ⁵ may be bonded to each other to form a cyclic structure, and Z represents a single bond or a divalent linking group.
It is also characterized by having the monomer (constituent unit derived from a monomer) shown by.
In the above formula (2), R ³ is preferably a methyl group among a hydrogen atom and a methyl group. In the above formula (2), R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. Here, in the present invention, the “hydrocarbon group” is a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and is any of linear, branched, and cyclic Form may be sufficient. The aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and the unsaturated bond can have an arbitrary position. As said aliphatic hydrocarbon group, a C1-C20 (preferably 1-12) aliphatic hydrocarbon group is preferable, More specifically, a C1-C20 (preferably 1-12) alkyl is preferable. Group, an alkenyl group having 2 to 20 carbon atoms (preferably 2 to 12 carbon atoms), and an alkynyl group having 2 to 20 carbon atoms (preferably 2 to 12 carbon atoms). Specifically, as the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, ter-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group Octyl group, decyl group, dodecyl group and the like. Examples of the alkenyl group include ethenyl, 1-propenyl, 1-butenyl, 1,3-butadienyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-ethyl-2- A butenyl group, a 2-octenyl group, a (4-ethenyl) -5-hexenyl group, a 2-decenyl group, and the like can be mentioned. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-butynyl group, and the like. A pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, 2-octynyl group, (4-ethynyl) -5-hexynyl group, 2-decynyl group and the like can be mentioned.

  Moreover, as said alicyclic hydrocarbon group, a C3-C20 (preferably 3-12) alicyclic hydrocarbon group is preferable, Specifically, C3-C20 (preferably 3-12). ), And more specifically, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, and the like can be given. Here, in the present invention, the “alicyclic hydrocarbon group” is a general term for carbocyclic compounds having a structure in which carbon atoms are bonded in a cyclic manner, excluding aromatic compounds, and the above-mentioned aliphatic carbonization. Those having a hydrogen group as a substituent or a linking group with a nitrogen atom and the like are also included. Further, the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), more specifically 6 to 20 carbon atoms (preferably 6 to 14 carbon atoms). Of the aryl group. Here, in the present invention, the “aryl group” refers to a monocyclic to tricyclic aromatic hydrocarbon group, and specifically includes a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an azulenyl group, and the like. Can do.

  Examples of the substituent in the hydrocarbon group include a halogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, phenoxy group and the like.

In the above formula (2), the single bond or divalent linking group (Z) is, for example, an alkanediyl group having 1 to 10 carbon atoms (preferably 1 to 6), 6 to 20 carbon atoms (preferably 6 to 6 carbon atoms). 14) an arylene group, a —CONH—R ⁶ — (* 1) group, a —COO—R ⁷ — (* 1) group, and the like. Here, R < ⁶ > and R < ⁷ > show a single bond, a C1-C10 (preferably 1-6) alkanediyl group, or a C2-C10 alkyleneoxyalkylene group mutually independently, * 1) indicates a bond that bonds with N. Examples of the alkanediyl group include a methylene group, an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, Propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, pentane-1,5 -Diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, etc. can be mentioned. Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. Examples of the alkyleneoxyalkylene group having 2 to 10 carbon atoms include an ethyleneoxyethylene group, an ethyleneoxypropylene group, a propyleneoxypropylene group, and an ethyleneoxybutylene group. Among them, Z is preferably a —COO—R ⁷ — (* 1) group, and R ⁷ is preferably an alkanediyl group having 2 to 6 carbon atoms.

  Moreover, as an unsaturated monomer containing the amino group which is an essential component of the polymer of the present invention, for example, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate are more preferable.

  The content ratio of the unsaturated monomer containing an amino group is preferably in the range of 0.5 to 55% by mass, more preferably 1 to 35% by weight, and still more preferably 1 to 15% by weight in all monomer components. % Should be good. If the content of the unsaturated monomer containing an amino group is less than 0.5% by mass, the dispersibility and stability of the coloring material may be insufficient. On the other hand, when the amount is more than 55% by mass, the viscosity of the polymer is increased and handling properties may be deteriorated or heat resistance may be insufficient.

  The monomer component for obtaining the polymer (A) is an unsaturated monomer having an acid group (preferably a carboxyl group), an unsaturated monomer having a hydroxyl group, or an amino group having an amino group, which are essential components. In addition to the saturated monomer, the monomer (d) represented by the following general formula (1) may be included as necessary.

(In formula (1), R ¹ and R ² each independently represents a hydrocarbon group selected from methyl, ethyl, cyclohexyl, and benzyl.)
In the general formula (1), R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, but methyl, ethyl In view of heat resistance, primary or secondary carbon substituents such as cyclohexyl, benzyl, etc., which are difficult to be removed by heat or heat, are preferred. Note that R ¹ and R ² may be the same type of substituent or different substituents.
The monomer represented by the general formula (1) (hereinafter sometimes referred to as “ether dimer” or “dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer”) is polymerized. In this case, it is presumed that the ether dimer is cyclized to form a tetrahydropyran ring structure in the structural unit of the polymer.

  (D) The structural unit derived from the monomer represented by the general formula (1) is considered to have the tetrahydropyran ring structure.

In the above general formula (1), it may have a substituent represented by R ¹ and R ² , for example, a linear or branched alkyl group such as methyl or ethyl; an alicyclic ring such as cyclohexyl An alkyl group substituted with an aryl group such as benzyl; and the like. From the standpoint of heat resistance, an acid such as methyl, ethyl, cyclohexyl and benzyl and a primary or secondary carbon substituent which is not easily removed by heat are preferred. Note that R ¹ and R ² may be the same type of substituent or different substituents.

  In addition to the structural unit derived from the ether dimer, the structural unit is derived from (e) a structural unit derived from an N-substituted maleimide monomer, and (f) a structural unit derived from an α- (unsaturated alkoxyalkyl) acrylate monomer. May contain at least one kind of structural unit.

  The (d) ether dimer, (e) N-substituted maleimide monomer, and (f) α- (unsaturated alkoxyalkyl) acrylate monomer are single monomers capable of introducing a ring structure into the main chain skeleton of the polymer. It is a mer. (E) N-substituted maleimide monomer is a monomer having a double bond-containing ring structure in the molecule, and (f) α- (unsaturated alkoxyalkyl) acrylate monomer is cyclopolymerized. It is a monomer that forms a polymer having a ring structure in the main chain.

  A polymer containing an N-substituted maleimide monomer unit and / or a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer unit has heat resistance and dispersibility (for example, colorant dispersibility). ), A cured film with improved hardness and the like can be provided. Moreover, the polymer containing an α- (unsaturated alkoxyalkyl) acrylate monomer unit is capable of contributing to plate-making properties such as adhesion, curability, and dry redissolvability, colorant dispersibility, heat resistance, It becomes possible to give a cured film with improved transparency and the like. In addition, as mentioned above, the polymer containing a monomer unit means, for example, a polymer containing a constituent unit derived from the monomer by a polymerization reaction or a crosslinking reaction of the monomer.

  Examples of the N-substituted maleimide monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide and the like can be mentioned, and one or more of these can be used. Among these, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable because of little coloring and excellent dispersibility.

  Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide Halogen-substituted benzylmaleimide such as o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide;

  Examples of the dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer include dimethyl-2,2 ′-[, from the viewpoints of little coloring, dispersibility, industrial availability, and the like. It is preferable to use oxybis (methylene)] bis-2-propenoate or the like.

  Examples of the α- (unsaturated alkoxyalkyl) acrylate monomer include α-allyloxymethyl acrylic acid, α-allyloxymethyl acrylate methyl, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl. N-propyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate n-amyl, α-allyloxymethyl acrylate s-amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate neopentyl, α-allyloxymethyl acrylate n -Hexyl, α-allyloxymethylacrylic acid s-hex , Α-allyloxymethyl acrylate n-heptyl, α-allyloxymethyl acrylate n-octyl, α-allyloxymethyl acrylate s-octyl, α-allyloxymethyl acrylate t-octyl, α-allyloxy 2-ethylhexyl methyl acrylate, capryl of α-allyloxymethyl acrylate, nonyl α-allyloxymethyl acrylate, decyl α-allyloxymethyl acrylate, undecyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid Lauryl, tridecyl α-allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-ary Chain saturated hydrocarbon groups such as stearyl oxymethyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, seryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate, etc. Containing α- (allyloxymethyl) acrylate is preferred. In addition, alkyl- (α-methallyloxymethyl) acrylate monomers and the like are also preferable. Among these, methyl α-allyloxymethyl acrylate (also referred to as α- (allyloxymethyl) methyl acrylate) is particularly preferable.

  The α- (unsaturated alkoxyalkyl) acrylate monomer can be produced by, for example, a production method disclosed in International Publication No. 2010/114077.

  Although the ratio of the (d) ether dimer is not particularly limited with respect to the total of all monomer components constituting the polymer, it is 2 to 60% by mass, preferably 5 to 55% by mass in the total monomer components. More preferably, it is 5 to 50% by mass. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight product during polymerization, or may be easily gelled. On the other hand, if the amount is too small, the transparency, heat resistance, etc. There is a risk that the coating performance will be insufficient.

  The ratio of the (e) N-substituted maleimide monomer and (f) α- (unsaturated alkoxyalkyl) acrylate monomer is not particularly limited as in the case of the ether dimer. 60 mass%, Preferably it is 5-55 mass%, More preferably, it is good that it is 5-50 mass%.

  The monomer component for obtaining the polymer (A) is an unsaturated monomer containing an essential acid group (preferably a carboxyl group), an unsaturated monomer containing a hydroxyl group, a general formula ( In addition to the ether dimer shown in 1), other copolymerizable monomers may be included as required. Other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n (meth) acrylate -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylic acid esters such as 1-adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. In addition, aromatic vinyl compounds such as styrene, vinyltoluene, and α-methylstyrene; alkyl-substituted maleimides such as N-methylmaleimide, N-isopropylmaleimide, and N-cyclohexylmaleimide, N-phenylmaleimide, N -Maleimide having an aromatic group such as benzylmaleimide; butadiene or substituted butadiene compound such as butadiene and isoprene; ethylene or substituted ethylene compound such as ethylene, propylene, vinyl chloride and acrylonitrile; vinyl esters such as vinyl acetate; Polymerization may be performed. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.

  The polymer of the present invention may further contain a polymerizable double bond in the side chain. By giving a polymerizable double bond to the side chain, it can be cured by heat or light. Therefore, the sensitivity to light when the photocurable resin composition is obtained is improved, the resin is cured with a smaller amount of light, and the mechanical strength after curing is also increased. Examples of the method for introducing a polymerizable double bond into the side chain include a method of adding a compound containing a polymerizable unsaturated double bond and at least one selected from the group consisting of an epoxy group, an oxazoline group, and a hydroxyl group. . As a polymerizable unsaturated double bond, the double bond which a (meth) acryloyl group has from a reactive point of the polymer obtained is mentioned preferably.

  Specific examples of the compound containing a polymerizable unsaturated double bond selected from the group consisting of an epoxy group, an oxazoline group, and a hydroxyl group include 2-hydroxyethyl (meth) acrylate and (meth) acrylic. Compounds having a hydroxyl group and a double bond such as 2-hydroxypropyl acid and allyl alcohol; Epoxy groups and a double bond such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and allyl glycidyl ether A compound having a double bond with an oxazoline group such as vinyl oxazoline and isopropenyl oxazoline; among these, among them, the reactivity is high, the reaction can be easily controlled, and the acquisition is easy. Not only radical polymerizable double bonds but also hydroxyl groups can be introduced at the same time From the point, glycidyl (meth) acrylate and (meth) acrylic acid 3, 4-epoxycyclohexyl methyl.

  The polymer of the present invention may further contain an epoxy group. Thereby, it can be cured by heat or light. In order to introduce an epoxy group into the polymer, for example, a monomer having an epoxy group may be polymerized as a monomer component. Examples of the monomer having an epoxy group include glycidyl methacrylate) and (meth) acrylic acid-3,4-epoxycyclohexyl. These monomers for introducing an epoxy group may be only one type or two or more types.

  When polymerizing the monomer component, a commonly used polymerization initiator may be added as necessary. Although it does not specifically limit as a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo compounds such as dimethyl 2,2′-azobis (2-methylpropionate), and the like. These polymerization initiators may be used alone or in combination of two or more. The amount of initiator used may be set as appropriate according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but the weight average molecular weight without gelation. Is from 0.1 to 15% by mass, more preferably from 0.5 to 10% by mass, based on the total monomer components, in that a polymer of several thousand to several tens of thousands can be obtained.

  When polymerizing the monomer component, a chain transfer agent that is usually used may be added, if necessary, for adjusting the molecular weight. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptopropionic acid, mercaptoacetic acid, and methyl mercaptoacetate, and α-methylstyrene dimer. Preferably, the chain transfer effect is high. N-dodecyl mercaptan and mercaptopropionic acid, which can reduce residual monomers and are easily available, are preferred. When a chain transfer agent is used, the amount used may be set as appropriate according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited. And 0.1 to 15% by mass, more preferably 0.5 to 10% by mass with respect to all monomer components, in that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained. Is preferred.

  The weight average molecular weight of the polymer is not particularly limited, but is preferably 2,000 to 200,000, more preferably 5,000 to 100,000. When the weight average molecular weight exceeds 200,000, the viscosity becomes too high to form a coating film, and when it is less than 2000, sufficient heat resistance tends to be hardly exhibited. The acid value of the polymer is preferably 20 to 300 mgKOH / g, more preferably 30 to 200 mgKOH / g. More preferably, it is 40-180 mgKOH / g. When the acid value of the polymer is less than 20 mgKOH / g, the solubility may be insufficient when the solubility by an alkaline substance is required. When it exceeds 300 mgKOH / g, it tends to be too viscous to form a coating film. The amine value of the polymer is preferably 1 to 200 mgKOH / g, more preferably 1 to 150 mgKOH / g. More preferably, it is 2-100 mgKOH / g. When the acid value of the polymer is less than 1 mgKOH / g, the dispersibility of the coloring material may be sufficient. When it exceeds 200 mgKOH / g, it may become difficult to form a coating film because of high viscosity, or the heat resistant colorability of the resin may be lowered.

In the case of introduction of the double bond, the double bond equivalent, which is the molecular weight per double bond of the polymer, is 350 to 4500 g / mol. 400 to 4000 is more preferable, and 500 to 3800 is most preferable. If the double bond equivalent is too high, the sensitivity to light may be low and developability may be lowered.If the double bond equivalent is too low, coloring may occur during curing, or storage stability may be deteriorated. There is a possibility that the solubility in a solvent is lowered.
The double bond equivalent is a measure of the amount of double bonds contained in the molecule. If the compounds have the same molecular weight, the larger the double bond equivalent value, the smaller the amount of double bonds introduced. Become. It can be calculated from the charged amount of a polymer or a compound introducing a double bond. Moreover, it can measure using various analysis, such as titration and elemental analysis, NMR, IR, and a differential scanning calorimeter method.

  The present invention is also a curable resin composition containing (A) the polymer and (B) a polyfunctional (meth) acrylate. Hereinafter, the polymer component (A) may be referred to as “(A) component” and the polyfunctional (meth) acrylate (B) may be referred to as “(B) component”. Although it is not limited as a use, it is used suitably for the material for forming protective films, such as a color filter, a liquid crystal display element, an integrated circuit element, a solid-state image sensor.

  In the curable resin composition, as (B) polyfunctional (meth) acrylate, for example, (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylol Propane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, di Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) ) A polyfunctional (meth) acrylate of tri- (meth) acrylate of isocyanurate. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are preferable.

  In the curable resin composition, light or a thermal polymerization initiator may be used when the curable resin composition is cured. Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2 -Propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butanone, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-) Acetophenones such as methylpionyl) benzyl] phenyl} -2-methylpropan-1-one; benzoin Benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,3 ′ , 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) Benzophenones such as ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone Thioxanthones such as 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride, and others Phenylglyoxylic methyl ester, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Among these, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone are preferable.

  For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, organic peroxides such as t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis And azo compounds such as (2,4-dimethylvaleronitrile) and dimethyl 2,2′-azobis (2-methylpropionate). These light and thermal polymerization initiators may be used alone or in combination of two or more.

  The curable resin composition of the present invention (preferably a negative curable resin composition) may contain a solvent as a diluent, if necessary. As the solvent, the polymer (A), the polyfunctional (meth) acrylate (B), and each component of the polymerization initiator to be contained as necessary are uniformly dissolved and do not react with each component. There is no particular limitation. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform and dimethyl sulfoxide; Etc. In addition, what is necessary is just to set content of a solvent suitably according to the optimal viscosity at the time of using a resin composition. For example, it is 900 parts by mass or less, more preferably 500 parts by mass or less with respect to 100 parts by mass of the resin. A preferable lower limit is 30 parts by mass or more, more preferably 60 parts by mass or more with respect to 100 parts by mass of the resin. By controlling to the above numerical range, the handleability and storage stability of the composition, and further the efficiency during the coating operation are improved.

  In addition to the polymer (A), the polyfunctional (meth) acrylate (B), the polymerization initiator, and the solvent, the curable resin composition of the present invention has a range that does not impair the effect of the present invention. Fillers such as aluminum hydroxide, talc, clay, barium sulfate, dyes, pigments, antifoaming agents, coupling agents, leveling agents, sensitizers, release agents, lubricants, plasticizers, antioxidants, UV absorbers Further, it may contain known additives such as a light stabilizer, a flame retardant, a polymerization inhibitor, a polymerization retarder, a polymerization accelerator, a thickener, a dispersant, and a surfactant. As the pigment, one or more of various organic or inorganic colorants can be used. As the organic colorant, dyes, organic pigments, natural pigments and the like can be used.

  The present invention is also a laminate in which a cured layer formed by curing the polymer and / or the curable resin composition is provided on a substrate. Examples of the material used as the substrate of the present invention include glass, acrylic resin, polycarbonate resin, polyester resin such as PET, transparent material such as polystyrene resin, and metal material such as aluminum, copper, iron, and stainless steel.

  The polymer of the present invention is excellent in transparency and heat resistance, and can be used for applications such as resist materials, various coating agents, paints, and the like, and since the polymer has a carboxyl group, it is a colored pixel of a color filter. In addition, it can be suitably used as an alkali development type negative resist material for producing a black matrix, an overcoat, a photospacer, an optical waveguide and the like. Since the polymer of the present invention has a better pigment dispersibility when it has a tetrahydropyran ring structure in its structure, it can be suitably used in a colored curable resin composition for a color filter.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Analysis in each synthesis example and comparative synthesis example was performed as follows.

<Weight average molecular weight>
It measured by polystyrene conversion using the gel permeation chromatograph measuring apparatus ("Shodex GPC System-21H" Showa Denko make).
<Polymer concentration in polymer solution>
A solution in which 4 g of acetone was added to 1 g of the polymer solution and dissolved was naturally dried at room temperature, further dried under reduced pressure (160 ° C./5 mmHg) for 5 hours, and then allowed to cool in a desiccator to measure the weight. Then, the nonvolatile content of the polymer solution was calculated from the weight loss, and this was used as the polymer concentration.
<Acid value>
To 0.5-1 g of the polymer solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly. An automatic titrator ("COM-555" Hiranuma Sangyo Co., Ltd.) uses 0.1 mol / L KOH aqueous solution as the titrant. And the acid value of the solution was measured. Then, the acid value of the polymer was calculated from the acid value of the solution and the polymer concentration.

<Amine number>
To 0.5-1 g of the polymer solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly. An automatic titrator ("COM-555" Hiranuma Sangyo Co., Ltd.) uses 0.1 mol / L HCl aqueous solution as the titrant. The amine value of the solution was measured. Then, the amine value of the polymer was calculated from the amine value of the solution and the polymer concentration.

<Example 1>
A separable flask equipped with a cooling tube was prepared as a reaction tank, and dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as “MD”) 20 mass as a monomer dropping tank. Parts, 15 parts by weight of methacrylic acid (hereinafter referred to as “MAA”), 10 parts by weight of 2-hydroxyethyl methacrylate (hereinafter referred to as “HEMA”), dimethylaminoethyl methacrylate (hereinafter referred to as “DAM”) 2.9 Parts by mass, cyclohexyl methacrylate (hereinafter referred to as “CHMA”) 40 parts by mass, methyl methacrylate (hereinafter referred to as “MMA”) 12.1 parts by mass, t-butylperoxy-2-ethylhexanoate (trade name) "Perbutyl O", manufactured by NOF Corporation; hereinafter referred to as "PBO") 3 parts by mass, propylene glycol monomethyl ether acetate 40 parts by mass of Tate (hereinafter referred to as “PGMEA”) was prepared by thoroughly stirring and mixing, and 4 parts by mass of n-dodecanethiol (hereinafter referred to as “n-DM”) and 32 parts by mass of PGMEA as a chain transfer agent dropping tank. Was prepared by thoroughly stirring and mixing. The reaction vessel was charged with 71 parts by mass of PGMEA and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed for 135 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, it was cooled to room temperature to obtain a polymer solution 1 having a concentration of 40% by mass. The weight average molecular weight of the polymer was 10,000, the acid value was 100 mgKOH / g, and the amine value was 10 mgKOH / g.

<Example 2>
A separable flask equipped with a cooling tube as a reaction tank was prepared. On the other hand, as a monomer dropping tank, MD 20 parts by mass, MAA 15 parts by mass, HEMA 20 parts by mass, DAM 5.8 parts by mass, CHMA 35 parts by mass, MMA 4.2 parts by mass, What prepared PTO3 mass part and PGMEA40 mass part well stirring and mixing was prepared, and what mixed well n-DM4 mass part and PGMEA32 mass part as a chain transfer agent dripping tank was prepared.
The reaction vessel was charged with 71 parts by mass of PGMEA and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed for 135 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a polymer solution 2 having a concentration of 40% by mass. The weight average molecular weight of the polymer was 10,000, the acid value was 100 mgKOH / g, and the amine value was 20 mgKOH / g.
<Comparative Example 1>
A separable flask with a cooling tube was prepared as a reaction tank, and as a monomer dropping tank, 20 parts by mass of MD, 15 parts by mass of MAA, 55 parts by mass of CHMA, 10 parts by mass of MMA, 3 parts by mass of PBO, and 40 parts by mass of PGMEA were well stirred and mixed. The thing prepared and what stir-mixed 4 mass parts of n-DM and 32 mass parts of PGMEA as a chain transfer agent dripping tank was prepared.
The reaction vessel was charged with 71 parts by mass of PGMEA and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed for 135 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a comparative polymer solution 1 having a concentration of 40% by mass. The weight average molecular weight of the polymer was 10,000, and the acid value was 100 mgKOH / g.
<Comparative Example 2>
A separable flask equipped with a cooling tube as a reaction tank was prepared. On the other hand, as a monomer dropping tank, MD 20 parts by mass, MAA 15 parts by mass, DAM 5.8 parts by mass, CHMA 55 parts by mass, MMA 4.2 parts by mass, PBO 3 parts by mass, What mixed and mixed 40 mass parts of PGMEA well was prepared, and what mixed well n-DM4 mass part and 32 mass parts of PGMEA as a chain transfer agent dripping tank was prepared.
The reaction vessel was charged with 71 parts by mass of PGMEA and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed for 135 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a comparative polymer solution 2 having a concentration of 40% by mass. The weight average molecular weight of the polymer was 10,000, the acid value was 100 mgKOH / g, and the amine value was 20 mgKOH / g.
<Heat resistance>
The test piece 1 was heated on a hot plate at 250 ° C. for 3 hours, cooled to room temperature, and then the b ^* value after the heat resistance test was measured using a spectrocolorimeter (“EE-6000” manufactured by Nippon Denshoku Industries Co., Ltd.). did.
<Appearance evaluation>
○: Unevenness is not seen in the coating film on the test piece 1 after the heat test.
X: Concavities and convexities are seen on the coating film on the test piece 1 after the heat resistance test.

<Example 3>
100 parts by mass of polymer solution 1 obtained in Example 1, 20 parts of dipentaerythritol hexaacrylate (trade name “Light Acrylate DPE-6A”, manufactured by Kyoeisha Chemical Co., Ltd .; hereinafter referred to as “DPE-6A”), 2 parts of a photoinitiator (trade name “Irgacure 907”, manufactured by Ciba-Geigy Co., Ltd .; hereinafter referred to as “Irg907”) and 55 parts of PGMEA were stirred and mixed uniformly to obtain a curable resin composition 1.

The obtained curable resin composition 1 was applied on a non-alkali glass plate using a spin coater so that the thickness after total drying was 3 μm, and dried on a hot plate at 100 ° C. for 3 minutes. Ultraviolet light was irradiated using an ultrahigh pressure mercury lamp so that the irradiation amount was 100 mJ / cm ² . After the irradiation, the test piece 1 was further dried at 230 ° C. for 30 minutes on a hot plate. And using this test piece 1, heat resistance was evaluated by said method. The b ^* value after the heat test was measured and found to be 2.7. When the appearance of the test piece 1 after the heat resistance test was observed, the coating film on the glass showed no unevenness and a film was uniformly formed.

<Example 4>
Except having changed the resin solution 1 to the resin solution 2, after preparing the curable resin composition 2 like Example 1, the test piece 2 was created similarly and heat resistance was evaluated. The b ^* value after the heat test was measured and found to be 3.0. When the appearance of the test piece 1 after the heat resistance test was observed, the coating film on the glass showed no unevenness and a film was uniformly formed.
<Comparative Example 3>
Except having changed the resin solution 1 to the resin solution 3, after preparing the curable resin composition 3 like Example 1, the comparative test piece 1 was created similarly and heat resistance was evaluated. When the b ^* value after the heat test was measured, it was 4.6 and it was yellowish compared to Example 3. When the appearance of the test piece 1 after the heat resistance test was seen, the coating film on the glass was uneven, and a skin-like film was formed.
<Comparative example 4>
Except having changed the polymer solution 1 into the polymer solution 4, after preparing the curable resin composition 4 like Example 1, the test piece 2 for a comparison is created similarly and heat resistance is evaluated. did. When the b ^* value after the heat resistance test was measured, it was 4.9, which was yellowish compared to Example 4. When the appearance of the test piece 1 after the heat resistance test was seen, the coating film on the glass was uneven, and a skin-like film was formed.

From these, (a) an unsaturated monomer having a carboxyl group, (b) an unsaturated monomer having a hydroxyl group, and (c) an unsaturated monomer having an amino group are polymerized as essential components. It was confirmed that the b ^* value after heat resistance in the cured product obtained from the polymer obtained was small.
From the above, it is possible to form an extremely excellent coating film with heat resistance and transparency for the first time by using the polymer having the above-described configuration. For example, it is suitable for applications such as resist materials, various coating agents and paints. Can be used. In addition, according to the present invention, for example, it is possible to provide a good quality color filter free from pattern defects and development residues.

  The polymer and resin composition of the present invention can form a coating film having excellent heat resistance and transparency as well as curability. For example, in applications such as resist materials, various coating agents, and paints It can be used suitably.

Claims (7)

(A) a structural unit derived from an unsaturated monomer having an acid group, (b) a structural unit derived from an unsaturated monomer having a hydroxyl group, and (c) a structural unit derived from an unsaturated monomer having an amino group. A curable resin composition comprising: a polymer containing as an essential component; and a polyfunctional (meth) acrylate. The curable resin composition according to claim 1, wherein the polymer has a ring structure in the main chain . The polymer is (d) the following general formula (1)

(In formula (1), R ¹ and R ² each independently represents a hydrocarbon group selected from methyl, ethyl, cyclohexyl, and benzyl.)
(E) a structural unit derived from an N-substituted maleimide monomer, and (f) a structural unit derived from an α- (unsaturated alkoxyalkyl) acrylate monomer. The curable resin composition according to claim 1, comprising at least one structural unit . The curable resin composition according to claim 1, wherein the polymer has an acid value of 20 to 300 mgKOH / g . The curable resin composition according to claim 1, wherein the polymer has an amine value of 1 to 200 mg KOH / g . In the polymer, the unsaturated monomer having an amino group is represented by the following general formula (2):

(In Formula (2), R ³ has a hydrogen atom or a methyl group, and R ^{4 to} R ⁵ each independently represent a hydrogen atom or a chain or cyclic carbonization optionally having a substituent. Represents a hydrogen group, and R ⁴ and R ⁵ may be bonded to each other to form a cyclic structure, and Z represents a single bond or a divalent linking group.
It is shown by these, The curable resin composition in any one of Claims 1-5 characterized by the above-mentioned . A laminate comprising a cured layer formed by curing the curable resin composition according to any one of claims 1 to 6 on a substrate.